Aromatic heterocyclic derivative, material for organic electroluminescent element, and organic electroluminescent element

ABSTRACT

An organic EL device includes an anode, an emitting layer, an electron transporting zone and a cathode in this sequence, in which the electron transporting zone contains an aromatic heterocyclic derivative represented by a formula (1) below. In the formula (1), X 1  to X 3  are a nitrogen atom or CR 1 , and A is represented by a formula (2) below. In the formula (2), L 1  is s single bond or a linking group, and HAr is represented by a formula (3) below. In the formula (3), Y 1  is an oxygen atom, a sulfur atom or the like, and one of X 11  to X 18  is a carbon atom bonded to L 1  by a single bond and the rest of X 11  to X 18  are a nitrogen atom or CR 13 .

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of prior U.S. applicationSer. No. 15/840,848, filed Dec. 13, 2017, the disclosure of which isincorporated herein by reference in its entirety. U.S. application Ser.No. 15/840,848 is a continuation application of prior U.S. applicationSer. No. 14/918,935, filed Oct. 21, 2015, issued as U.S. Pat. No.9,893,296 on Feb. 13, 2018, the disclosure of which is incorporatedherein by reference in its entirety. U.S. application Ser. No.14/918,935 is a continuation application of prior U.S. application Ser.No. 13/989,698, filed May 24, 2013, issued as U.S. Pat. No. 9,209,406 onDec. 8, 2015, the disclosure of which is incorporated herein byreference in its entirety. U.S. application Ser. No. 13/989,698 is theNational Stage of PCT/JP12/080156, filed Nov. 21, 2012, the disclosureof which is incorporated herein by reference in its entirety. U.S.application Ser. No. 13/989,698 claims priority to Japanese ApplicationNo. 2011-255472, filed Nov. 22, 2011, and to Japanese Application No.2012-193349, filed Sep. 3, 2012, the disclosures of which areincorporated herein by reference in their entireties.

FIELD

Embodiment(s) described herein relates to an organic electroluminescencedevice, an aromatic heterocyclic derivative applicable to the organicelectroluminescence device, and an organic-electroluminescence-devicematerial including the aromatic heterocyclic derivative.

BACKGROUND

An organic electroluminescence device (hereinafter, occasionallyreferred to as an organic EL device) can be classified by the emissionprinciple into two types: a fluorescent organic EL device and aphosphorescent organic EL device. When a voltage is applied to theorganic EL device, holes are injected from an anode and electrons areinjected from a cathode. The holes and the electrons are recombined inan emitting layer to form excitons. According to the electron spinstatistics theory, singlet excitons and triplet excitons are generatedat a ratio of 25%:75%. In a fluorescent organic EL device which usesemission caused by singlet excitons, the limited value of an internalquantum efficiency is believed to be 25%. A technology for extending alifetime of a fluorescent organic EL device using a fluorescent materialhas recently been improved and applied to a full-color display of amobile phone, TV and the like. However, as compared with aphosphorescent organic EL device, a fluorescent organic EL device isrequired to be improved in efficiency.

In contrast, in relation to a technology of manufacturing a highlyefficient fluorescent-organic-EL device, there has been disclosed atechnology of extracting emissions derived from triplet excitons by aphenomenon (i.e., TTF (Triplet-Triplet Fusion) phenomenon) in which twotriplet excitons collide and fuse with each other to generate singletexcitons. A blocking layer that effectively induces the TTF phenomenonrequires to be made of a highly electron-resistant compound serving as alayer for transporting electrons as well as having a wide gap forincreasing triplet energy. In view of this point, a compound formed of ahydrocarbon ring has been considered suitable.

Patent Literature 1 discloses an organic EL device having a pyreneskeleton or an anthracene skeleton and further a substituent selectedfrom a carbazolyl group, dibenzofuranyl group or dibenzothiophenyl groupin an electron transporting layer adjacent to a fluorescent emittinglayer.

Patent Literature 2 discloses an organic-EL device using a fluoranthenederivative for a blocking layer in order to effectively induce The TTFphenomenon.

CITATION LIST Patent Literatures

Patent Literature 1: International Publication No. WO2010/001817

Patent Literature 2: International Publication No. WO2010/134350

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

An object of the invention is to provide an organic EL device that emitsat a high efficiency and is driven at a lower drive voltage, an aromaticheterocyclic derivative applicable to the organic EL device, and anorganic-EL-device material including the aromatic heterocyclicderivative.

Means for Solving the Problems

[1] An organic electroluminescence device according to an aspect of theinvention includes: an anode; an emitting layer; an electrontransporting zone; and a cathode in this sequence, in which the electrontransporting zone comprises an aromatic heterocyclic derivativerepresented by a formula (1) below.

In the formula (1), X₁ to X₃ are a nitrogen atom or CR₁, with a provisothat at least one of X₁ to X₃ is a nitrogen atom;

R₁ independently represents a hydrogen atom, a halogen atom, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, a substituted or unsubstituted heterocyclic group having 5to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to30 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 30 carbon atoms, a substituted or unsubstituted alkynyl group having2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl grouphaving 3 to 30 carbon atoms, a substituted or unsubstituted arylsilylgroup having 6 to 30 ring carbon atoms, a substituted or unsubstitutedalkoxy group having 1 to 30 carbon atoms, a substituted or unsubstitutedaralkyl group having 6 to 30 ring carbon atoms, or a substituted orunsubstituted aryloxy group having 6 to 30 ring carbon atoms.

In the formula (1), A is represented by a formula (2) below.[Formula 2](HAr)_(a)-L₁-  (2)

In the formula (2), HAr is represented by a formula (3) below.

In the formula (2), a is an integer of 1 to 5.

When a is 1, L₁ is a single bond or a divalent linking group.

When a is in a range of 2 to 5, L₁ is a trivalent to hexavalent linkinggroup and HAr is the same or different.

The linking group is a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms, or a residue having 2 to 6 valences inducedfrom any one of a group formed by bonding two or three of thesubstituted or unsubstituted aryl group having 6 to 30 ring carbon atomsand the substituted or unsubstituted heterocyclic group having 5 to 30ring atoms.

The mutually bonded groups are the same or different.

In the formula (3), X₁₁ to X₁₈ each are independently a nitrogen atom,CR₁₃ or a carbon atom bonded to L₁ by a single bond.

In the formula (3), Y₁ is a nitrogen atom, a sulfur atom, SiR₁₁R₁₂ or asilicon atom bonded to each of R₁₁ and L₁ by a single bond.

L₁ is bonded by one of a carbon atom at X₁₁ to X₁₈ and R₁₁ to R₁₂ and asilicon atom at Y₁.

R₁₁ and R₁₂ represent the same as R₁ in the formula (1). R₁₁ and R₁₂ arethe same or different.

R₁₃ independently represents a hydrogen atom, a halogen atom, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, a substituted or unsubstituted heterocyclic group having 5to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to30 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 30 carbon atoms, a substituted or unsubstituted alkynyl group having2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl grouphaving 3 to 30 carbon atoms, a substituted or unsubstituted arylsilylgroup having 6 to 30 ring carbon atoms, a substituted or unsubstitutedalkoxy group having 1 to 30 carbon atoms, a substituted or unsubstitutedaralkyl group having 6 to 30 ring carbon atoms, or a substituted orunsubstituted aryloxy group having 6 to 30 ring carbon atoms. Aplurality of R₁₃ are mutually the same or different. Adjacent R₁₃ maybond to each other to form a ring.

In the above formula (1), Ar₁ and Ar₂ each are independently representedby the formula (2), or represent a substituted or unsubstituted arylgroup having 6 to 30 ring carbon atoms or a substituted or unsubstitutedheterocyclic group having 5 to 30 ring atoms.

[2] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (3), X₁₃ or X₁₆ is a carbon atombonded to L₁ by a single bond.

[3] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (3), X₁₁ or X₁₈ is a carbon atombonded to L₁ by a single bond.

[4] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (2), a is an integer of 1 to 3.

[5] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (2), a is 1 or 2.

[6] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (2), a is 1, L₁ is a linkinggroup, and the linking group is a divalent residue of a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, or a divalentresidue of a substituted or unsubstituted heterocyclic group having 5 to30 ring atoms.

[7] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (2), a is 2 and L₁ is a linkinggroup, and the linking group is a trivalent residue of a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, or atrivalent residue of a substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms.

[8] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (3), Y₁ is an oxygen atom or asulfur atom.

[9] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (3), Y₁ is an oxygen atom or asulfur atom, and one of X₁₁ to X₁₈ is a carbon atom bonded to L₁ by asingle bond and the rest of X₁₁ to X₁₈ are CR₁₃.

[10] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (1), two or three of X₁ to X₃are a nitrogen atom.

[11] In the organic electroluminescence device according to the aboveaspect of the invention, in the formula (2), L₁ is a divalent ortrivalent residue induced from any one of benzene, biphenyl, terphenyl,naphthalene and phenanthrene.

[12] In the organic electroluminescence device according to the aboveaspect of the invention, the electron transporting zone includes ablocking layer, the blocking layer including the aromatic heterocyclicderivative represented by the formula (1).

[13] The organic electroluminescence device according to the aboveaspect of the invention further includes at least one of an electroninjecting layer and an electron transporting layer between the blockinglayer and the cathode, in which the at least one of the electroninjecting layer and the electron transporting layer includes at leastone of an electron-donating dopant material and an organic metalcomplex.

[14] In the organic electroluminescence device according to the aboveaspect of the invention, the electron-donating dopant material is atleast one material selected from the group consisting of an alkalimetal, an alkaline-earth metal, a rare earth metal, an alkali metaloxide, an alkali metal halogenide, an alkaline-earth metal oxide, analkaline-earth metal halogenide, a rare earth metal oxide and a rareearth metal halogenide, and the organic metal complex is at least onecomplex selected from the group consisting of an organic metal complexcomprising an alkali metal, an organic metal complex comprising analkaline-earth metal, and an organic metal complex comprising arare-earth metal.

[15] In the organic electroluminescence device according to the aboveaspect of the invention, the emitting layer is in contact with theelectron transporting zone comprising the aromatic heterocyclicderivative.

[16] In the organic electroluminescence device according to the aboveaspect of the invention, the emitting layer includes an anthracenederivative represented by a formula (20D) below.

In the formula (20D), Ar¹¹ and Ar¹² each independently represent asubstituted or unsubstituted monocyclic group having 5 to 30 ring atoms,a substituted or unsubstituted fused cyclic group having 10 to 30 ringatoms or a group formed by combining the monocyclic group and the fusedcyclic group.

In the formula (20D), R¹⁰¹ to R¹⁰⁸ each independently represent ahydrogen atom, a halogen atom, a cyano group, a substituted orunsubstituted monocyclic group having 5 to 30 ring atoms, a substitutedor unsubstituted fused cyclic group having 10 to 30 ring atoms, a groupformed by combining the monocyclic group and the fused cyclic group, asubstituted or unsubstituted alkyl group having 1 to 30 carbon atoms, asubstituted or unsubstituted cycloalkyl group having 3 to 30 ring carbonatoms, a substituted or unsubstituted alkylsilyl group having 3 to 30carbon atoms, a substituted or unsubstituted arylsilyl group having 8 to30 ring carbon atoms, a substituted or unsubstituted alkoxy group having1 to 30 carbon atoms, a substituted or unsubstituted aralkyl grouphaving 7 to 30 carbon atoms, a substituted or unsubstituted aryloxygroup having 6 to 30 ring carbon atoms, or a substituted orunsubstituted silyl group.

[17] In the organic electroluminescence device according to the aboveaspect of the invention, the emitting layer includes a fluorescentdopant material having a main peak wavelength of 500 nm or less.

An aromatic heterocyclic derivative according to another aspect of theinvention is represented by a formula (4) below.

In the formula (4), X₁ to X₃ are a nitrogen atom or CR₁, with a provisothat at least one of X₁ to X₃ is a nitrogen atom.

R₁ independently represents a hydrogen atom, a halogen atom, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, a substituted or unsubstituted heterocyclic group having 5to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to30 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 30 carbon atoms, a substituted or unsubstituted alkynyl group having2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl grouphaving 3 to 30 carbon atoms, a substituted or unsubstituted arylsilylgroup having 6 to 30 ring carbon atoms, a substituted or unsubstitutedalkoxy group having 1 to 30 carbon atoms, a substituted or unsubstitutedaralkyl group having 6 to 30 ring carbon atoms, or a substituted orunsubstituted aryloxy group having 6 to 30 ring carbon atoms.

In the formula (4), A is represented by a formula (5) below.[Formula 6](HAr)_(a)-L₁-  (5)

In the formula (5), HAr is represented by a formula (6) below.

In the formula (5), a is an integer of 1 to 5.

When a is 1, L₁ is a divalent linking group.

When a is in a range of 2 to 5, L₁ is a trivalent to hexavalent linkinggroup and HAr is the same or different.

The linking group is a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms, or a residue having 2 to 6 valences inducedfrom any one of a group formed by bonding two or three of thesubstituted or unsubstituted aryl group having 6 to 30 ring carbon atomsand the substituted or unsubstituted heterocyclic group having 5 to 30ring atoms.

The mutually bonded groups are the same or different.

In the formula (6), Y₁ is an oxygen atom or a sulfur atom.

In the formula (6), X₁₁ and X₁₈ are a nitrogen atom or CR₁₃.

In the formula (6), one of X₁₂ to X₁₇ is a carbon atom bonded to L₁ by asingle bond and the rest of X₁₂ to X₁₇ are a nitrogen atom or CR₁₃.

R₁₃ independently represents a hydrogen atom, a halogen atom, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, a substituted or unsubstituted heterocyclic group having 5to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to30 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 30 carbon atoms, a substituted or unsubstituted alkynyl group having2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl grouphaving 3 to 30 carbon atoms, a substituted or unsubstituted arylsilylgroup having 6 to 30 ring carbon atoms, a substituted or unsubstitutedalkoxy group having 1 to 30 carbon atoms, a substituted or unsubstitutedaralkyl group having 6 to 30 ring carbon atoms, or a substituted orunsubstituted aryloxy group having 6 to 30 ring carbon atoms.

A plurality of R₁₃ are mutually the same or different. Adjacent R₁₃ maybond to each other to form a ring.

In the above formula (4), Ar₁ and Ar₂ each are independently representedby the formula (5), or represent a substituted or unsubstituted arylgroup having 6 to 30 ring carbon atoms or a substituted or unsubstitutedheterocyclic group having 5 to 30 ring atoms.

[19] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, in the formula (6), X₁₃ or X₁₆ is a carbon atombonded to L₁ by a single bond.

[20] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, in the formula (5), a is an integer of 1 to 3.

[21] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, in the formula (5), a is 1 or 2.

[22] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, in the formula (5), a is 1 and L₁ is a linkinggroup, and the linking group is a divalent residue of a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, or a divalentresidue of a substituted or unsubstituted heterocyclic group having 5 to30 ring atoms.

[23] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, in the formula (5), a is 2 and L₁ is a linkinggroup, and the linking group is a trivalent residue of a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, or atrivalent residue of a substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms.

[24] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, in the formula (6), Y₁ is an oxygen atom.

[25] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, in the formula (6), Y₁ is an oxygen atom, X₁₁and X₁₈ are CR₁₃, and one of X₁₂ to X₁₇ is a carbon atom bonded to L₁ bya single bond and the rest of X₁₂ to X₁₇ are CR₁₃.

[26] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, In the formula (4), two or three of X₁ to X₃are a nitrogen atom.

[27] In the aromatic heterocyclic derivative according to the aboveaspect of the invention, In the formula (5), L₁ is a divalent ortrivalent residue induced from any one of benzene, biphenyl, terphenyl,naphthalene and phenanthrene.

[28] An organic-electroluminescence-device material according to furtheraspect of the invention includes the aromatic heterocyclic derivativeaccording to the above aspect of the invention.

According to the embodiment(s), an organic EL device that emits at ahigh efficiency and is driven at a lower drive voltage, an aromaticheterocyclic derivative applicable to the organic EL device, and anorganic-EL-device material including the aromatic heterocyclicderivative can be provided.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a view showing one example of an organic EL device accordingto a first exemplary embodiment of the invention.

FIG. 2 is a view showing a relationship of energy gaps between layers ofthe invention.

FIG. 3 is a view showing an action based on the relationship of theenergy gaps between the layers of the invention.

FIG. 4 is an energy band diagram showing a case where an affinity of ahost material (Ah)> an affinity of a dopant material (Ad) is satisfied.

FIG. 5 is an energy band diagram showing a case where Ah<Ad is satisfiedand a difference between Ah and Ad is less than 0.2 eV.

FIG. 6 is an energy band diagram showing a case where Ah<Ad is satisfiedand a difference between Ah and Ad is more than 0.2 eV.

FIG. 7 is an energy band diagram showing a case where a dopant materialsatisfying Ah<Ad and a dopant material satisfying Ah>Ad coexist.

FIG. 8 is a view showing one example of an organic EL device accordingto a second exemplary embodiment of the invention.

FIG. 9 is a view showing one example of an organic EL device accordingto a third exemplary embodiment of the invention.

FIG. 10 is a view showing one example of an organic EL device accordingto a third exemplary embodiment of the invention.

FIG. 11 is a view showing one example of an organic EL device accordingto a fifth exemplary embodiment of the invention.

FIG. 12 is a view showing one example of an organic EL device accordingto a sixth exemplary embodiment of the invention.

FIG. 13 is a view showing a measurement system of transitional EL waves.

FIG. 14A is a view showing a measurement method of a ratio of luminousintensity derived from TTF and is a graph showing a change over time ofluminous intensity of the EL device.

FIG. 14B is a view showing a measurement method of a ratio of theluminous intensity derived from TTF and is a graph showing a change overtime of a reciprocal square root of the luminous intensity.

DESCRIPTION OF EMBODIMENTS

Aromatic Heterocyclic Derivative

An aromatic heterocyclic derivative according to an exemplary embodimentis represented by a formula (4) below.[Formula 8]

In the formula (4), X₁ to X₃ are a nitrogen atom or CR₁.

However, at least one of X₁ to X₃ is a nitrogen atom.

R₁ independently represents a hydrogen atom, halogen atom, cyano group,substituted or unsubstituted aryl group having 6 to 30 ring carbonatoms, substituted or unsubstituted heterocyclic group having 5 to 30ring atoms, substituted or unsubstituted alkyl group having 1 to 30carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to30 carbon atoms, substituted or unsubstituted arylsilyl group having 6to 30 ring carbon atoms, substituted or unsubstituted alkoxy grouphaving 1 to 30 carbon atoms, substituted or unsubstituted aralkyl grouphaving 6 to 30 ring carbon atoms, or substituted or unsubstitutedaryloxy group having 6 to 30 ring carbon atoms.

In the formula (4), A is represented by a formula (5) below.[Formula 9](HAr)_(a)-L₁-  (5)

In the formula (5), HAr is represented by a formula (6) below.

In the formula (5), a is an integer of 1 to 5.

When a is 1, L₁ is a divalent linking group.

When a is in a range of 2 to 5, L₁ is a trivalent to hexavalent linkinggroup and HAr is the same or different.

The linking group is a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms, or a divalent to hexavalent residue inducedfrom any one of a group formed by bonding two or three of the abovegroups.

The mutually bonded groups are the same or different.

In the formula (6), Y₁ is an oxygen atom or a sulfur atom.

In the formula (6), X₁₁ and X₁₈ are a nitrogen atom or CR₁₃.

In the formula (6), one of X₁₂ to X₁₇ is a carbon atom bonded to L₁ by asingle bond and the rest of X₁₂ to X₁₇ are a nitrogen atom or CR₁₃.

R₁₃ independently represents a hydrogen atom, halogen atom, cyano group,substituted or unsubstituted aryl group having 6 to 30 ring carbonatoms, substituted or unsubstituted heterocyclic group having 5 to 30ring atoms, substituted or unsubstituted alkyl group having 1 to 30carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to30 carbon atoms, substituted or unsubstituted arylsilyl group having 6to 30 ring carbon atoms, substituted or unsubstituted alkoxy grouphaving 1 to 30 carbon atoms, substituted or unsubstituted aralkyl grouphaving 6 to 30 ring carbon atoms, or substituted or unsubstitutedaryloxy group having 6 to 30 ring carbon atoms. A plurality of R₁₃ aremutually the same or different. Adjacent R₁₃ may bond to each other toform a ring.

In the above formula (4), Ar₁ and Ar₂ each are independently representedby the formula (5), or represent a substituted or unsubstituted arylgroup having 6 to 30 ring carbon atoms or a substituted or unsubstitutedheterocyclic group having 5 to 30 ring atoms.

In the formula (6), X₁₃ or X₁₆ is preferably a carbon atom bonded to L₁by a single bond.

In the formula (5), a is an integer in a range of 1 to 5, morepreferably of 1 to 3, particularly preferably 1 or 2.

When a is 1, L₁ is a divalent linking group and the formula (5) isrepresented by a formula (5-1).

When a is in a range of 2 to 5, L₁ is a trivalent to hexavalent linkinggroup. When a is 2, L₁ is a trivalent linking group and the formula (5)is represented by a formula (5-2). At this time, HAr is the same ordifferent.

The linking group is a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms, or a divalent or trivalent residue inducedfrom any one of a group formed by bonding two or three of the abovegroups.

In L₁ of the formulae (5), (5-1) and (5-2), the group formed by bondingtwo or three of the above groups means a group formed by bonding, with asingle bond, two or three of the divalent or trivalent residue inducedfrom the aryl group having 6 to 30 ring carbon atoms and theheterocyclic group having 5 to 30 ring atoms. In the linking group, themutually bonded groups are the same or different.

In the formulae (5), (5-1) and (5-2), L₁ is preferably a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, orsubstituted or unsubstituted heterocyclic group having 5 to 30 ringatoms.

Moreover, in the formulae (5), (5-1) and (5-2), L₁ is more preferably adivalent or trivalent residue induced from any one of benzene, biphenyl,terphenyl, naphthalene and phenanthrene.

In the formula (5), it is more preferable that a is 1 and L₁ is adivalent residue of a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, or a divalent residue of a substituted orunsubstituted heterocyclic group having 5 to 30 ring atoms.

In the formula (5), it is more preferable that a is 2 and L₁ is alinking group, specifically, a trivalent residue of a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, or atrivalent residue of a substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms.

In the formula (6), X₁₃ or X₁₆ is preferably a carbon atom bonded to L₁by a single bond.

In the formula (6), Y₁ is preferably an oxygen atom.

Moreover, in the formula (6), it is more preferable that Y₁ is an oxygenatom, X₁₁ and X₁₈ are CR₁₃, one of X₁₂ to X₁₇ is a carbon atom bonded toL₁ by a single bond and the rest of X₁₂ to X₁₇ are CR₁₃.

In the formula (4), two or three of X₁ to X₃ are preferably a nitrogenatom.

Ar₁, Ar₂, L₁, R₁, R₁₁ to R₁₃ in the formulae (4) to (6) and (5-1) to(5-2) will be described below.

Examples of the aryl group having 6 to 30 ring carbon atoms in theformulae (4) to (6) and (5-1) to (5-2) are a phenyl group, 1-naphthylgroup, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthrylgroup, benzanthryl group, 1-phenanthryl group, 2-phenanthryl group,3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group,naphthacenyl group, pyrenyl group, 1-chrysenyl group, 2-chrysenyl group,3-chrysenyl group, 4-chrysenyl group, 5-chrysenyl group, 6-chrysenylgroup, benzo[c]phenanthryl group, benzo[g]chrysenyl group,1-triphenylenyl group, 2-triphenylenyl group, 3-triphenylenyl group,4-triphenylenyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenylgroup, 4-fluorenyl group, 9-fluorenyl group, benzofluorenyl group,dibenzofluorenyl group, 2-biphenylyl group, 3-biphenylyl group,4-biphenylyl group, o-terphenyl group, m-terphenyl-4-yl group,m-terphenyl-3-yl group, m-terphenyl-2-yl group, p-terphenyl-4-yl group,p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-quarter-phenyl group,3-fluoranthenyl group, 4-fluoranthenyl group, 8-fluoranthenyl group,9-fluoranthenyl group, benzofluoranthenyl group, o-tolyl group, m-tolylgroup, p-tolyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group,mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group,p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group,4′-methylbiphenylyl group, 4″-t-butyl-p-terphenyl-4-yl group,9,9-dimethyl-1-fluorenyl group, 9,9-dimethyl-2-fluorenyl group,9,9-dimethyl-3-fluorenyl group, 9,9-dimethyl-4-fluorenyl group,9,9-diphenyl-1-fluorenyl group, 9,9-diphenyl-2-fluorenyl group,9,9-diphenyl-3-fluorenyl group, and 9,9-diphenyl-4-fluorenyl group.

The aryl group in the formulae (4) to (6) and (5-1) to (5-2) preferablyhas 6 to 20 ring carbon atoms, more preferably 6 to 12 ring carbonatoms. Among the aryl group, a phenyl group, biphenyl group, naphthylgroup, phenanthryl group, terphenyl group, fluorenyl group andtriphenylenyl group are particularly preferable. In 1-fluorenyl group,2-fluorenyl group, 3-fluorenyl group and 4-fluorenyl group, a carbonatom at the ninth position is preferably substituted by the substitutedor unsubstituted alkyl group having 1 to 30 carbon atoms in the formula(4).

Examples of the heterocyclic group having 5 to 30 ring atoms in theformulae (4) to (6) and (5-1) to (5-2) are a pyrroyl group, pyrazinylgroup, pyridinyl group, indolyl group, isoindolyl group, imidazolylgroup, furyl group, benzofuranyl group, isobenzofuranyl group,dibenzofuranyl group, dibenzothiophenyl group, quinolyl group,isoquinolyl group, quinoxalinyl group, carbazolyl group, phenanthridinylgroup, acridinyl group, phenanthrolinyl group, phenazinyl group,phenothiazinyl group, phenoxazinyl group, oxazolyl group, oxadiazolylgroup, furazanyl group, thienyl group, benzothiophenyl group and a groupformed from a pyridine ring, pyrazine ring, pyrimidine ring, pyridazinering, triazine ring, indole ring, quinoline ring, acridine ring,pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring,piperadine ring, carbazole ring, furan ring, thiophene ring, oxazolering, oxadiazole ring, benzooxazole ring, thiazole ring, thiadiazolering, benzothiazole ring, triazole ring, imidazole ring, benzoimidazolering, pyrane ring and dibenzofuran ring.

Specific examples of the heterocyclic group having 5 to 30 ring atoms inthe formulae (4) to (6) and (5-1) to (5-2) are a 1-pyrroyl group,2-pyrroyl group, 3-pyrroyl group, pyrazinyl group, 2-pyridinyl group,2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group,6-pyrimidinyl group, 1,2,3-triazine-4-yl group, 1,2,4-triazine-3-ylgroup, 1,3,5-triazine-2-yl group, 1-imidazolyl group, 2-imidazolylgroup, 1-pyrazolyl group, 1-indolidinyl group, 2-indolidinyl group,3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group,7-indolidinyl group, 8-indolidinyl group, 2-imidazopyridinyl group,3-imidazopyridinyl group, 5-imidazopyridinyl group, 6-imidazopyridinylgroup, 7-imidazopyridinyl group, 8-imidazopyridinyl group, 3-pyridinylgroup, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolylgroup, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolylgroup, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group,4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolylgroup, 2-furyl group, 3-furyl group, 2-benzofuranyl group,3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group,6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group,3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranylgroup, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolylgroup, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolylgroup, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group,3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group,6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group,2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group,1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolylgroup, 9-carbazolyl group, azacarbazolyl-1-yl group, azacarbazolyl-2-ylgroup, azacarbazolyl-3-yl group, azacarbazolyl-4-yl group,azacarbazolyl-5-yl group, azacarbazolyl-6-yl group, azacarbazolyl-7-ylgroup, azacarbazolyl-8-yl group, azacarbazolyl-9-yl group,1-phenanthrydinyl group, 2-phenanthrydinyl group, 3-phenanthridinylgroup, 4-phenanthrydinyl group, 6-phenanthrydinyl group,7-phenanthrydinyl group, 8-phenanthrydinyl group, 9-phenanthrydinylgroup, 10-phenanthrydinyl group, 1-acridinyl group, 2-acridinyl group,3-acridinyl group, 4-acridinyl group, 9-acridinyl group,1,7-phenanthroline-2-yl group, 1,7-phenanthroline-3-yl group,1,7-phenanthroline-4-yl group, 1,7-phenanthroline-5-yl group,1,7-phenanthroline-6-yl group, 1,7-phenanthroline-8-yl group,1,7-phenanthroline-9-yl group, 1,7-phenanthroline-10-yl group,1,8-phenanthroline-2-yl group, 1,8-phenanthroline-3-yl group,1,8-phenanthroline-4-yl group, 1,8-phenanthroline-5-yl group,1,8-phenanthroline-6-yl group, 1,8-phenanthroline-7-yl group,1,8-phenanthroline-9-yl group, 1,8-phenanthroline-10-yl group,1,9-phenanthroline-2-yl group, 1,9-phenanthroline-3-yl group,1,9-phenanthroline-4-yl group, 1,9-phenanthroline-5-yl group,1,9-phenanthroline-6-yl group, 1,9-phenanthroline-7-yl group,1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-yl group,1,10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group,1,10-phenanthroline-4-yl group, 1,10-phenanthroline-5-yl group,2,9-phenanthroline-1-yl group, 2,9-phenanthroline-3-yl group,2,9-phenanthroline-4-yl group, 2,9-phenanthroline-5-yl group,2,9-phenanthroline-6-yl group, 2,9-phenanthroline-7-yl group,2,9-phenanthroline-8-yl group, 2,9-phenanthroline-10-yl group,2,8-phenanthroline-1-yl group, 2,8-phenanthroline-3-yl group,2,8-phenanthroline-4-yl group, 2,8-phenanthroline-5-yl group,2,8-phenanthroline-6-yl group, 2,8-phenanthroline-7-yl group,2,8-phenanthroline-9-yl group, 2,8-phenanthroline-10-yl group,2,7-phenanthroline-7-yl group, 2,7-phenanthroline-3-yl group,2,7-phenanthroline-4-yl group, 2,7-phenanthroline-5-yl group,2,7-phenanthroline-6-yl group, 2,7-phenanthroline-1-yl group,2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group,1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl-phenylgroup, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinylgroup, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinylgroup, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group,2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienylgroup, 3-thienyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-ylgroup, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group,3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group,3-methylpyrrole-4-yl group, 3-methylpyrrole-5-yl group,2-t-butylpyrrole-4-yl group, 3-(2-phenylpropyl)pyrrole-1-yl group,2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolylgroup, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group,4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group,4-t-butyl-3-indolyl group, 1-dibenzofuranyl group, 2-dibenzofuranylgroup, 3-dibenzofuranyl group, 4-dibenzofuranyl group,1-dibenzothiophenyl group, 2-dibenzothiophenyl group,3-dibenzothiophenyl group, 4-dibenzothiophenyl group, 1-silafluorenylgroup, 2-silafluorenyl group, 3-silafluorenyl group, 4-silafluorenylgroup, 1-germafluorenyl group, 2-germafluorenyl group, 3-germafluorenylgroup and 4-germafluorenyl group.

The heterocyclic group in the formulae (4) to (6) and (5-1) to (5-2)preferably has 5 to 20 ring atoms, more preferably 5 to 14 ring atoms.Among the heterocyclic group, 1-dibenzofuranyl group, 2-dibenzofuranylgroup, 3-dibenzofuranyl group, 4-dibenzofuranyl group,1-dibenzothiophenyl group, 2-dibenzothiophenyl group,3-dibenzothiophenyl group, 4-dibenzothiophenyl group, 2-pyridinyl group,2-imidazopyridinyl group, 3-imidazopyridinyl group, 5-imidazopyridinylgroup, 6-imidazopyridinyl group, 7-imidazopyridinyl group,8-imidazopyridinyl group, 3-pyridinyl group, 4-pyridinyl group,1-imidazolyl group, 2-imidazolyl group, 2-quinolyl group, 3-quinolylgroup, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolylgroup, 8-quinolyl group, phenanthrolinyl group, and a group formed froma triazine ring or a benzoimidazole ring are preferable.

The alkyl group having 1 to 30 carbon atoms in the formulae (4) and (6)may be linear, branched or cyclic. Examples of the linear or branchedalkyl group are a methyl group, ethyl group, propyl group, isopropylgroup, n-butyl group, s-butyl group, isobutyl group, t-butyl group,n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonylgroup, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecylgroup, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group,n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentylgroup, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group,1-heptyloctyl group, 3-methylpentyl group, hydroxymethyl group,1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group,1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group,2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethylgroup, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group,1,2-dichloroethyl group, 1,3-dichloroisopropyl group,2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethylgroup, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group,1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butylgroup, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropylgroup, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropylgroup, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group,cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropylgroup, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group,nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,1,2-dinitroethyl group, 2,3-dinitro-t-butyl group, and1,2,3-trinitropropyl group.

Examples of the cyclic alkyl group (cycloalkyl group) are a cyclopropylgroup, cyclobutyl group, cyclopentyl group, cyclohexyl group,4-methylcyclohexyl group, 1-adamantyl group, 2-adamantyl group,1-norbornyl group, and 2-norbornyl group.

The linear or branched alkyl group in the formulae (4) and (6)preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbonatoms. Among the linear or branched alkyl group, a methyl group, ethylgroup, propyl group, isopropyl group, n-butyl group, s-butyl group,isobutyl group, t-butyl group, n-pentyl group and n-hexyl group arepreferable.

The cycloalkyl group in the formulae (4) and (6) preferably has 3 to 10ring carbon atoms, more preferably 5 to 8 ring carbon atoms. Among thecycloalkyl group, a cyclopentyl group and a cyclohexyl group arepreferable.

A halogenated alkyl group provided by substituting the alkyl group witha halogen atom is exemplified by a halogenated alkyl group provided bysubstituting the alkyl group having 1 to 30 carbon atoms with one ormore halogen groups. Specific examples of the halogenated alkyl groupare a fluoromethyl group, difluoromethyl group, trifluoromethyl group,fluoroethyl group and trifluoromethylethyl group.

The alkenyl group having 2 to 30 carbon atoms in the formulae (4) and(6) may be linear, branched or cyclic. Examples of the alkenyl group arevinyl, propenyl, butenyl, oleyl, eicosapentaenyl, docosahexaenoyl,styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, and2-phenyl-2-propenyl. Among the alkenyl group, a vinyl group ispreferable.

The alkynyl group having 2 to 30 carbon atoms in the formulae (4) and(6) may be linear, branched or cyclic. Examples of the alkynyl group areethynyl, propynyl, and 2-phenylethynyl. Among the alkynyl group, anethynyl group is preferable.

The alkylsilyl group having 3 to 30 carbon atoms in the formulae (4) and(6) is exemplified by a trialkylsilyl group having the examples of thealkyl group having 1 to 30 carbon atoms. Specific examples of thealkylsilyl group are a trimethylsilyl group, triethylsilyl group,tri-n-butylsilyl group, tri-n-octylsilyl group, triisobutylsilyl group,dimethylethylsilyl group, dimethylisopropylsilyl group,dimethyl-n-propylsilyl group, dimethyl-n-butylsilyl group,dimethyl-t-butylsilyl group, diethylisopropylsilyl group,vinyldimethylsilyl group, propyldimethylsilyl group andtriisopropylsilyl group. Three alkyl groups may be the same ordifferent.

The arylsilyl group having 6 to 30 ring carbon atoms in the formulae (4)and (6) may be a dialkylarylsilyl group, alkyldiarylsilyl group andtriarylsilyl group.

The dialkylarylsilyl group is exemplified by a dialkylarylsilyl grouphaving two of the examples of the alkyl group having 1 to 30 carbonatoms and one of the aryl group having 6 to 30 ring carbon atoms. Thedialkylarylsilyl group preferably has 8 to 30 carbon atoms. Two alkylgroups may be the same or different.

The alkyldiarylsilyl group is exemplified by an alkyldiarylsilyl grouphaving one of the examples of the alkyl group having 1 to 30 carbonatoms and two of the aryl group having 6 to 30 ring carbon atoms. Thedialkylarylsilyl group preferably has 13 to 30 carbon atoms. Two arylgroups may be the same or different.

The triarylsilyl group is exemplified by a triarylsilyl group havingthree of the aryl group having 6 to 30 ring carbon atoms. Thedialkylarylsilyl group preferably has 18 to 30 carbon atoms. Three arylgroups may be the same or different.

The alkoxy group having 1 to 30 carbon atoms in the formulae (4) and (6)is represented by —OY. Y is exemplified by the alkyl group having 1 to30 carbon atoms. Examples of the alkoxy group are a methoxy group,ethoxy group, propoxy group, butoxy group, pentyloxy group and hexyloxygroup.

A halogenated alkoxy group provided by substituting the alkoxy groupwith a halogen atom is exemplified by a halogenated alkoxy groupprovided by substituting the alkoxy group having 1 to 30 carbon atomswith one or more halogen groups.

The aralkyl group having 6 to 30 ring carbon atoms in the formulae (4)and (6) is represented by —Y—Z. Y is exemplified by an alkylene groupcorresponding to the alkyl group having 1 to 30 carbon atoms. Z isexemplified by the examples of the aryl group having 6 to 30 ring carbonatoms. This aralkyl group is preferably an aralkyl group having 7 to 30carbon atoms, in which an aryl moiety has 6 to 30 carbon atoms,preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms,and an alkyl moiety has 1 to 30 carbon atoms, preferably 1 to 20 carbonatoms, more preferably 1 to 10 carbon atoms, further preferably 1 to 6carbon atoms. Examples of the aralkyl group are a benzyl group,2-phenylpropane-2-yl group, 1-phenylethyl group, 2-phenylethyl group,1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group,á-naphthylmethyl group, 1-á-naphthylethyl group, 2-á-naphthylethylgroup, 1-á-naphthylisopropyl group, 2-á-naphthylisopropyl group,â-naphthylmethyl group, 1-â-naphthylethyl group, 2-â-naphthylethylgroup, 1-â-naphthylisopropyl group, 2-â-naphthylisopropyl group,1-pyrrolylmethyl group, 2-(1-pyrroyl)ethyl group, p-methylbenzyl group,m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group,m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group,m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group,m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group,m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group,m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group,m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group,m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropylgroup and 1-chloro-2-phenylisopropyl group.

The aryloxy group having 6 to 30 ring carbon atoms in the formulae (4)and (6) is represented by —OZ. Z is exemplified by the aryl group having6 to 30 ring carbon atoms or the following monocyclic group and fusedcyclic group. The aryloxy group is exemplified by a phenoxy group.

Examples of the halogen atom in the formulae (4) and (6) are fluorine,chlorine, bromine and iodine, among which fluorine is preferable.

In the invention, “carbon atoms forming a ring (ring carbon atoms)” meancarbon atoms forming a saturated ring, unsaturated ring, or aromaticring. “Atoms forming a ring (ring atoms)” mean carbon atoms and heteroatoms forming a hetero ring including a saturated ring, unsaturatedring, or aromatic ring.

Examples of the substituent meant by “substituted or unsubstituted” arethe above-described aryl group, heterocyclic group, alkyl group (linearor branched alkyl group, cycloalkyl group and halogenated alkyl group),alkenyl group, alkynyl group, alkylsilyl group, arylsilyl group, alkoxygroup, halogenated alkoxy group, aralkyl group, aryloxy group, halogenatom, cyano group, hydroxyl group, nitro group and carboxy group. In theabove-described substituents, the aryl group, heterocyclic group, alkylgroup, halogen atom, alkylsilyl group, arylsilyl group and cyano groupare preferable. The preferable ones of the specific examples of eachsubstituent are further preferable. Moreover, these substituents may befurther substituted by the above-described substituents.

“Unsubstituted” in “substituted or unsubstituted” means that a hydrogenatom is substituted.

In a later-described compound or a partial structure thereof, the sameapplies to the description of “substituted or unsubstituted.”

In the invention, a “hydrogen atom” means isotopes having differentneutron numbers and specifically encompasses protium, deuterium andtritium.

Examples of specific structures of the aromatic heterocyclic derivativeaccording to this exemplary embodiment represented by the formula (4)are as follows. However, the invention is not limited to the aromaticderivative having these structures.

Organic-EL-Device Material

The aromatic heterocyclic derivative of the invention is usable as anorganic-EL-device material. The organic-EL-device material may onlycontain the aromatic heterocyclic derivative of the invention, oralternatively, may further contain another compound. Theorganic-EL-device material containing the aromatic heterocyclicderivative according to the exemplary embodiment is usable, forinstance, as a material for an electron transporting zone, e.g., amaterial for a blocking layer. It should be noted that, in theinvention, the electron transporting zone means any one of an electrontransporting layer, an electron injecting layer and a blocking layer, orcombination of two or more thereof.

Organic EL Device First Exemplary Embodiment

This exemplary embodiment utilizes TTF phenomenon. The TTF phenomenonwill be initially described below.

Holes and electrons respectively injected from an anode and a cathodeare recombined in an emitting layer to generate excitons. As for thespin state, as is conventionally known, singlet excitons account for 25%and triplet excitons account for 75%. In a conventionally knownfluorescent device, light is emitted when singlet excitons of 25% arerelaxed to the ground state. The remaining triplet excitons of 75% arereturned to the ground state without emitting light through a thermaldeactivation process. Accordingly, the theoretical limit value of theinternal quantum efficiency of a conventional fluorescent device isbelieved to be 25%.

The behavior of triplet excitons generated within an organic substancehas been theoretically examined. According to S. M. Bachilo et al. (J.Phys. Chem. A, 104, 7711 (2000)), assuming that high-order excitons suchas quintet excitons are quickly returned to triplet excitons, tripletexcitons (hereinafter abbreviated as ³A*) collide with one another withan increase in the density thereof, whereby a reaction shown by thefollowing formula occurs. In the formula, ¹A represents the ground stateand ¹A* represents the lowest singlet excitons.³A*+³A*→( 4/9)¹A+( 1/9)¹A*+(13/9)³A*

In other words, 5³A*→4¹A+¹A*, and it is expected that, among tripletexcitons initially generated, which account for 75%, one fifth thereof(i.e., 20%) is changed to singlet excitons. Accordingly, the amount ofsinglet excitons which contribute to emission is 40%, which is a valueobtained by adding 15% (75%×(⅕)=15%) to 25%, which is the amount ratioof initially generated singlet excitons. At this time, a ratio ofluminous intensity derived from TTF (TTF ratio) relative to the totalluminous intensity is 15/40, i.e., 37.5%. Assuming that singlet excitonsare generated by collision of initially-generated triplet excitons whichaccount for 75% (i.e., one singlet exciton is generated from two tripletexcitons), a significantly high internal quantum efficiency of 62.5% isobtained which is a value obtained by adding 37.5% (75%×(½)=37.5%) to25%, which is the amount ratio of initially generated singlet excitons.At this time, the TTF ratio is 60% (37.5/62.5).

FIG. 1 is schematic view showing one example of an organic EL deviceaccording to a first exemplary embodiment of the invention. FIG. 2 is aview showing a relationship between a triplet energy of the emittinglayer and a triplet energy of an electron transporting zone in theorganic EL device according to the first exemplary embodiment. In theexemplary embodiment, the triplet energy is referred to as a differencebetween energy in the lowest triplet state and energy in the groundstate. The singlet energy (occasionally referred to as energy gap) isreferred to as a difference between energy in the lowest singlet stateand energy in the ground state.

An organic EL device 1 shown in FIG. 1 includes an anode 10, a holetransporting zone 60, an emitting layer 20, an electron transportingzone 70, and a cathode 50 in sequential order. These components areadjacent to one another in the organic EL device 1 in the exemplaryembodiment. The electron transporting zone 70 in the exemplaryembodiment includes a blocking layer 30 and an electron injecting layer40. It is preferred that the hole transporting zone 60 is interposedbetween the anode 10 and the emitting layer 20. The hole transportingzone includes at least one of a hole injecting layer and a holetransporting layer.

In the invention, a simply-called blocking layer means a layerfunctioning as a barrier against triplet energy. Accordingly, theblocking layer functions differently from a hole blocking layer and acharge blocking layer.

The emitting layer includes a host material and a dopant material. Thedopant material is preferably a dopant material exhibiting fluorescence(hereinafter, also referred to as a fluorescent dopant material). Afluorescent dopant material having a main peak wavelength of 550 nm orless is preferable. A fluorescent dopant material having a main peakwavelength of 500 nm or less is more preferable. A main peak wavelengthmeans a peak wavelength of luminescence spectrum exhibiting a maximumluminous intensity among luminous spectra measured in a toluene solutionwith a concentration from 10⁻⁵ mol/liter to 10⁻⁶ mol/liter. The mainpeak wavelength of 550 nm is substantially equivalent to a greenemission. In this wavelength zone, improvement in luminous efficiency ofa fluorescent device utilizing the TTF phenomenon is desired. In ablue-emitting fluorescent device of 480 nm or less, further improvementin luminous efficiency is expectable. In a red-emitting fluorescentdevice of 550 nm or more, a phosphorescent device exhibiting a highinternal quantum efficiency has already been at a practical level.Accordingly, improvement in luminous efficiency as a fluorescent deviceis not desired.

In FIG. 2, the holes injected from the anode are injected to theemitting layer via the hole transporting zone. The electrons injectedfrom the cathode are injected to the emitting layer via the electroninjecting layer and the blocking layer. Subsequently, the holes and theelectrons are recombined in the emitting layer to generate singletexcitons and triplet excitons. There are two manners as for theoccurrence of recombination: recombination may occur either on hostmaterial molecules or on dopant material molecules.

In this exemplary embodiment, as shown in FIG. 2, when the tripletenergy of the host material and that of the dopant material arerespectively taken as E^(T) _(h) and E^(T) _(d), a relationship of thefollowing formula (2A) is satisfied.E ^(T) _(h) <E ^(T) _(d)  (2A)

When this relationship of the formula (2A) is satisfied, tripletexcitons generated by recombination on the host material do not transferto the dopant material which has a higher triplet energy, as shown inFIG. 3. Triplet excitons generated by recombination on dopant materialmolecules quickly energy-transfer to host material molecules. In otherwords, triplet excitons on the host material do not transfer to thedopant material but collide with one another efficiently on the hostmaterial to generate singlet excitons by the TTF phenomenon. Moreover,since the singlet energy E^(S) _(d) of the dopant material is smallerthan the singlet energy E^(S) _(h) of the host material, a relationshipof the following formula (2B) is satisfied.E ^(S) _(d) <E ^(S) _(h)  (2B)

Since the relationship of the formula (2B) is satisfied, the singletexcitons generated by the TTF phenomenon energy-transfer from the hostmaterial to the dopant material, thereby contributing to fluorescence ofthe dopant material. In the dopant material which is usually used in afluorescent device, transition from the triplet state to the groundstate should be inhibited. In such a transition, triplet excitons arenot optically energy-deactivated, but are thermally energy-deactivated.By causing the triplet energy of a host material and the triplet energyof a dopant material to satisfy the above-mentioned relationship,singlet excitons are generated efficiently due to the collision oftriplet excitons before they are thermally deactivated, whereby luminousefficiency is improved. As a consequence, luminous efficiency isimproved.

In the exemplary embodiment, the blocking layer is adjacent to theemitting layer. The blocking layer has a function of preventing tripletexcitons generated in the emitting layer to be diffused to the electrontransporting zone and confining the triplet excitons within the emittinglayer to increase a density of the triplet excitons therein, therebycausing the TTF phenomenon efficiently.

The blocking layer also serves for efficiently injecting the electronsto the emitting layer. When the electron injecting properties to theemitting layer are deteriorated, the density of the triplet excitons isdecreased since the electron-hole recombination in the emitting layer isdecreased. When the density of the triplet excitons is decreased, thefrequency of collision of the triplet excitons is reduced, whereby theTTF phenomenon does not occur efficiently.

The blocking layer of the organic EL device according to the exemplaryembodiment contains an aromatic heterocyclic derivative represented by aformula (1) below.

In the formula (1), X₁ to X₃ are a nitrogen atom or CR₁.

However, at least one of X₁ to X₃ is a nitrogen atom.

R₁ independently represents a hydrogen atom, a halogen atom, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, a substituted or unsubstituted heterocyclic group having 5to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to30 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 30 carbon atoms, a substituted or unsubstituted alkynyl group having2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl grouphaving 3 to 30 carbon atoms, a substituted or unsubstituted arylsilylgroup having 6 to 30 ring carbon atoms, a substituted or unsubstitutedalkoxy group having 1 to 30 carbon atoms, a substituted or unsubstitutedaralkyl group having 6 to 30 ring carbon atoms, and a substituted orunsubstituted aryloxy group having 6 to 30 ring carbon atoms.

In the formula (1), A is represented by a formula (2) below.[Formula 68](HAr)_(a)-L₁-  (2)In the formula (2), HAr is represented by a formula (3) below.

In the formula (2), a is an integer of 1 to 5.

When a is 1, L₁ is a single bond or a divalent linking group.

When a is in a range of 2 to 5, L₁ is a trivalent to hexavalent linkinggroup and HAr is the same or different.

The linking group is a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms, or a residue having 2 to 6 valences inducedfrom any one of a group formed by bonding two or three of the abovegroups.

The mutually bonded groups are the same or different.

In the formula (3), X₁₁ to X₁₈ each are independently a nitrogen atom,CR₁₃ or a carbon atom bonded to L₁ by a single bond.

In the formula (3), Y₁ is a nitrogen atom, a sulfur atom, SiR₁₁R₁₂ or asilicon atom bonded to each of R₁₁ and L₁ by a single bond.

However, L₁ is bonded by one of a carbon atom at X₁ to X₁₈ and R₁₁ toR₁₂ and a silicon atom at Y₁.

R₁₁ and R₁₂ represent the same as R₁ in the formula (1). R₁₁ and R₁₂ arethe same or different.

R₁₃ independently represents a hydrogen atom, a halogen atom, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, a substituted or unsubstituted heterocyclic group having 5to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to30 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 30 carbon atoms, a substituted or unsubstituted alkynyl group having2 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl grouphaving 3 to 30 carbon atoms, a substituted or unsubstituted arylsilylgroup having 6 to 30 ring carbon atoms, a substituted or unsubstitutedalkoxy group having 1 to 30 carbon atoms, a substituted or unsubstitutedaralkyl group having 6 to 30 ring carbon atoms, or a substituted orunsubstituted aryloxy group having 6 to 30 ring carbon atoms. Aplurality of R₁₃ are mutually the same or different. Adjacent R₁₃ maybond to each other to form a ring.

In the above formula (1), Ar₁ and Ar₂ each are independently representedby the formula (2), or represent a substituted or unsubstituted arylgroup having 6 to 30 ring carbon atoms or a substituted or unsubstitutedheterocyclic group having 5 to 30 ring atoms.

In the formula (3), X₁₃ or X₁₆ is preferably a carbon atom bonded to L₁by a single bond. Alternatively, in the formula (3), X₁₁ or X₁₈ ispreferably a carbon atom bonded to L₁ by a single bond.

In the formula (2), a is an integer in a range of 1 to 5, morepreferably of 1 to 3, particularly preferably 1 or 2.

When a is 1, L₁ is a single bond or a divalent linking group and theformula (2) is represented by a formula (2-1) below.

When a is in a range of 2 to 5, L₁ is a trivalent to hexavalent linkinggroup. When a is 2, the formula (2) is represented by a formula (2-2)below. At this time, HAr is the same or different.

The linking group is a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms, or a divalent or trivalent residue inducedfrom any one of a group formed by bonding two or three of the abovegroups.

The group formed by bonding two or three of the above groups means agroup formed by bonding, with a single bond, two or three of thedivalent or trivalent residue induced from the aryl group having 6 to 30ring carbon atoms and the heterocyclic group having 5 to 30 ring atoms.In the linking group, the mutually bonded groups are the same ordifferent.

In the formulae (2), (2-1) and (2-2), L₁ is preferably a linking group.The linking group is a substituted or unsubstituted aryl group having 6to 30 ring carbon atoms, substituted or unsubstituted heterocyclic grouphaving 5 to 30 ring atoms, or a divalent or trivalent residue inducedfrom any one of a group formed by bonding two or three of the abovegroups. Further, the linking group is preferably a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, orsubstituted or unsubstituted heterocyclic group having 5 to 30 ringatoms.

In the formula (2), it is preferable that when a is 1 (see the formula(2-1)) and L₁ is a linking group, the linking group is a divalentresidue of a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, or a divalent residue of a substituted or unsubstitutedheterocyclic group having 5 to 30 ring atoms. More specifically, L₁ ispreferably a divalent residue induced from any one of benzene, biphenyl,terphenyl, naphthalene and phenanthrene.

In the formula (2), it is preferable that when a is 2 (see the formula(2-2)) and L₁ is a linking group, the linking group is a trivalentresidue of a substituted or unsubstituted aryl group having 6 to 30 ringcarbon atoms, or a trivalent residue of a substituted or unsubstitutedheterocyclic group having 5 to 30 ring atoms. More specifically, L₁ ispreferably a divalent residue induced from any one of benzene, biphenyl,terphenyl, naphthalene and phenanthrene.

In the formula (3), Y₁ is preferably an oxygen atom or a sulfur atom.Moreover, in the formula (3), it is preferable that Y₁ is an oxygen atomor a sulfur atom, one of X₁₁ to X₁₈ is a carbon atom bonded to L₁ by asingle bond and the rest of X₁₁ to X₁₈ are CR₁₃.

In the formula (1), two or three of X₁ to X₃ are more preferably anitrogen atom.

In the formula (2), L₁ is preferably a divalent or trivalent residueinduced from any one of benzene, biphenyl, terphenyl, naphthalene andphenanthrene.

Specific examples of each group for Ar¹, Ar², L₁, R₁, R₁₁ to R₁₃, X₁₁ toX₁₈ and Y₁ in the formulae (1) to (3) and (2-1) to (2-2) are the groupsdescribed in relation to the aromatic heterocyclic derivativerepresented by the formula (4).

Examples of specific structures of the aromatic heterocyclic derivativerepresented by the formula (1) and contained in the blocking layer ofthe organic EL device according to this exemplary embodiment are asfollows. However, the exemplary embodiment is not limited to thearomatic derivative having these structures.

The organic EL device 1 in the exemplary embodiment includes theelectron injecting layer 40 between the blocking layer 30 and thecathode 50 as described above. The electron injecting layer 40preferably contains the aromatic heterocyclic derivative represented bythe formula (1). Herein, the aromatic heterocyclic derivative containedin the blocking layer 30 and the aromatic heterocyclic derivativecontained in the electron injecting layer 40 may be the same ordifferent.

The electron injecting layer facilitates electron injection from thecathode. Specifically, for instance, the electron injecting layer may beprovided by a laminate of a typical electron transporting material andat least one of an electron-donating dopant material and an organicmetal complex. Alternatively, the electron injecting layer may beprovided by adding at least one of the electron-donating dopant materialand the organic metal complex to a material for forming the blockinglayer, specifically, in a vicinity of an interface of the electroninjecting layer to the cathode.

The electron-donating dopant material may be at least one selected froman alkali metal, an alkali metal compound, an alkaline-earth metal, analkaline-earth metal compound, a rare-earth metal, a rare-earth metalcompound and the like.

The organic metal complex may be at least one selected from an organicmetal complex including an alkali metal, an organic metal complexincluding an alkaline-earth metal, an organic metal complex including arare-earth metal, and the like.

Examples of the alkali metal are lithium (Li) (work function: 2.93 eV),sodium (Na) (work function: 2.36 eV), potassium (K) (work function: 2.28eV), rubidium (Rb) (work function: 2.16 eV) and cesium (Cs) (workfunction: 1.95 eV), which particularly preferably has a work function of2.9 eV or less. Among the above, the alkali metal is preferably K, Rb orCs, more preferably Rb or Cs, the most preferably Cs.

Examples of the alkaline-earth metal are calcium (Ca) (work function:2.9 eV), strontium (Sr) (work function: 2.0 to 2.5 eV), and barium (Ba)(work function: 2.52 eV), among which a substance having a work functionof 2.9 eV or less is particularly preferable.

Examples of the rare-earth metal are scandium (Sc), yttrium (Y), cerium(Ce), terbium (Tb), and ytterbium (Yb), among which a substance having awork function of 2.9 eV or less is particularly preferable.

Since the above preferred metals have particularly high reducibility,addition of a relatively small amount of the metals to an electroninjecting zone can enhance luminance intensity and lifetime of theorganic EL device.

Examples of the alkali metal compound are an alkali oxide such aslithium oxide (Li₂O), cesium oxide (Cs₂O) and potassium oxide (K₂O), andan alkali halogenide such as sodium fluoride (NaF), cesium fluoride(CsF) and potassium fluoride (KF), among which lithium fluoride (LiF),lithium oxide (Li₂O) and sodium fluoride (NaF) are preferable.

Examples of the alkaline-earth metal compound are barium oxide (BaO),strontium oxide (SrO), calcium oxide (CaO) and a mixture thereof, i.e.,barium strontium oxide (Ba_(x)Sr_(1-x)O) (0<x<1), barium calcium oxide(Ba_(x)Ca_(1-x)O) (0<x<1), among which BaO, SrO and CaO are preferable.

Examples of the rare earth metal compound are ytterbium fluoride (YbF₃),scandium fluoride (ScF₃), scandium oxide (ScO₃), yttrium oxide (Y₂O₃),cerium oxide (Ce₂O₃), gadolinium fluoride (GdF₃) and terbium fluoride(TbF₃), among which YbF₃, ScF₃, and TbF₃ are preferable.

The organic metal complex is not specifically limited as long ascontaining at least one metal ion of an alkali metal ion, analkaline-earth metal ion and a rare earth metal ion. A ligand for eachof the complexes is preferably quinolinol, benzoquinolinol, acridinol,phenanthridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole,hydroxydiaryl oxadiazole, hydroxydiaryl thiadiazole, hydroxyphenylpyridine, hydroxyphenyl benzoimidazole, hydroxybenzo triazole, hydroxyfluborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin,cyclopentadiene, β-diketones, azomethines, or a derivative thereof, butthe ligand is not limited thereto.

The electron-donating dopant material and the organic metal complex areadded to preferably form a layer or an island pattern in an interfacialregion. A layer or an island pattern of the electron-donating dopant andthe organic metal complex is preferably formed by evaporating at leastone of the electron-donating dopant material and the organic metalcomplex by resistance heating evaporation while an emitting material forforming the interfacial region or an organic substance as anelectron-injecting material are simultaneously evaporated, so that atleast one of the electron-donating dopant material and an organic metalcomplex reduction-causing dopant is dispersed in the organic substance.Dispersion concentration at which the electron-donating dopant isdispersed in the organic substance is a mole ratio (the organicsubstance to the electron-donating dopant or the organic metal complex)of 100:1 to 1:100, preferably 5:1 to 1:5.

When at least one of the electron-donating dopant material and theorganic metal complex forms a layer, the emitting material or theelectron injecting material for forming the organic layer of theinterfacial region is initially layered, and then, at least one of theelectron-donating dopant material and the organic metal complex issingularly evaporated thereon by resistance heating evaporation topreferably form a layer having a thickness of 0.1 nm to 15 nm.

When at least one of the electron-donating dopant material and theorganic metal complex forms an island pattern, the emitting material orthe electron injecting material for forming the organic layer of theinterfacial region is initially layered, and then, at least one of theelectron-donating dopant material is singularly evaporated thereon byresistance heating evaporation to preferably form an island patternhaving a thickness of 0.05 nm to 1 nm.

A ratio of the main component to at least one of the electron-donatingdopant material and the organic metal complex in the organic EL deviceaccording to the exemplary embodiment is preferably a mole ratio (themain component to the electron-donating dopant or the organic metalcomplex) of 5:1 to 1:5, more preferably 2:1 to 1:2.

A compound other than the electron-donating dopant material and theorganic metal complex, which is used in the electron injecting layer, isexemplified by a compound represented by the following formula (EIL-1).

In the formula (EIL-1), HAr¹ is a substituted or unsubstitutednitrogen-containing heterocyclic group, preferably having the followingstructures.

Examples of a substituent for HAr¹ in the formula (EIL-1) are a fluorineatom, a cyano group, a substituted or unsubstituted alkyl group having 1to 20 carbon atoms, a substituted or unsubstituted cycloalkyl grouphaving 3 to 20 carbon atoms, a substituted or unsubstituted alkylsilylgroup having 3 to 20 carbon atoms, a substituted or unsubstitutedarylsilyl group having 8 to 30 carbon atoms, a substituted orunsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted orunsubstituted aryloxy group having 6 to 30 carbon atoms, a substitutedor unsubstituted aryl group having 6 to 30 ring carbon atoms, or asubstituted or unsubstituted heterocyclic group having 5 to 30 ringatoms.

In the formula (EIL-1), Ar¹ is a substituted or unsubstituted fusedcyclic group having 10 to 30 ring carbon atoms, preferably having thefollowing fused cyclic structures.

Examples of a substituent for Ar¹ in the formula (EIL-1) are a fluorineatom, a cyano group, a substituted or unsubstituted alkyl group having 1to 20 carbon atoms, a substituted or unsubstituted cycloalkyl grouphaving 3 to 20 carbon atoms, a substituted or unsubstituted alkylsilylgroup having 3 to 20 carbon atoms, a substituted or unsubstitutedarylsilyl group having 8 to 30 carbon atoms, a substituted orunsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted orunsubstituted aryloxy group having 6 to 30 carbon atoms, a substitutedor unsubstituted aryl group having 6 to 30 ring carbon atoms, or asubstituted or unsubstituted heterocyclic group having 5 to 30 ringatoms.

L¹ in the formula (EIL-1) represents a single bond, a substituted orunsubstituted a+b valent aromatic hydrocarbon ring group having 6 to 30ring carbon atoms, a substituted or unsubstituted a+b valentheterocyclic group having 5 to 30 ring atoms, a substituted orunsubstituted hydrocarbon ring group having 6 to 30 ring carbon atoms,or an a+b valent group formed by bonding a plurality of substituted orunsubstituted heterocyclic groups having 5 to 30 ring atoms.

Examples of a substituent for L in the formula (EIL-1) are a fluorineatom, a cyano group, a substituted or unsubstituted alkylsilyl grouphaving 3 to 20 carbon atoms, a substituted or unsubstituted arylsilylgroup having 8 to 30 carbon atoms, a substituted or unsubstituted arylgroup having 6 to 30 ring carbon atoms, or a substituted orunsubstituted heterocyclic group having 5 to 30 ring atoms.

In the formula (EIL-1), a is an integer of 1 to 3, preferably a=1.

In the formula (EIL-1), b is an integer of 1 to 3, preferably b=1.

A compound used for the electron injecting layer is exemplified by acompound represented by the following formula (EIL-2).

In the formula (EIL-2), one of R₁₀₁ to R₁₀₈ is bonded to L² by a singlebond. The rest of R₁₀₁ to R₁₀₈ are a hydrogen atom or a substituent.

Examples of the substituent for R₁₀₁ to R₁₀₈ in the formula (EIL-2) arethe same as those listed in the formula (EIL-1). A preferred example isan alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to30 ring carbon atoms.

In the formula (EIL-2), L² represents a single bond or a linking group,in which the linking group is a c-valent aromatic hydrocarbon group orc-valent group having a structure represented by the following formula(EIL-2-1).

In the formula (EIL-2-1), R₁₀₉ to R₁₁₀ are a hydrogen atom or asubstituent.

In the formula (EIL-2-1), d and e are independently an integer of 1 to5.

In the formula (EIL-2-1), X is selected from the following structures.

In the formula (EIL-2), c is an integer of 2 to 4, preferably c is 2.

Among the compounds represented by the formula (EIL-2), a compoundbonded to L² in R₁₀₁ and represented by the following formula (EIL-2-2)is preferable.

In the formula (EIL-2-2), R₁₀₂ to R₁₀₇ are a hydrogen atom or asubstituent, preferably a hydrogen atom.

In the formula (EIL-2-2), c and L² are the same as those in the formula(EIL-2).

In the formula (EIL-2-2), c is preferably 2.

In the formula (EIL-2-2), L² is preferably a substituted orunsubstituted phenylene group or a substituted or unsubstitutednaphthylene group.

In the formula (EIL-2-2), Ar¹⁰⁸ represents a hydrogen atom, alkyl grouphaving 1 to 20 carbon atoms, or substituted or unsubstituted aryl grouphaving 6 to 30 ring carbon atoms, more preferably a methyl group,t-butyl group, substituted or unsubstituted phenyl group, or substitutedor unsubstituted naphthyl group.

In order to efficiently cause The TTF phenomenon, it is preferable toadjust a relationship between an affinity of the host material and anaffinity of the dopant material as described below. Hereinafter, theaffinity of the host material is described as A_(h), the affinity of thedopant material as A_(d), ionization potential of the host material asI_(h) and ionization potential of the dopant material as I_(d).

Now, the following cases will be described.

[1] Case of A_(h)>A_(d)

[2] Case of A_(h)<A_(d)

[3] Case where a dopant material satisfying A_(h)<A_(d) and a dopantmaterial satisfying A_(h)>A_(d) coexist

[1] Case of A_(h)>A_(d)

A case where a relationship of A_(h)>A_(d) is satisfied will bedescribed. The dopant material used in this exemplary embodiment is adopant material emitting fluorescence of a main peak wavelength of 550nm or less and exhibiting a relatively large energy gap. Accordingly,when the relationship of A_(h)>A_(d) is satisfied, a relationship ofI_(h)>I_(d) is simultaneously satisfied. Consequently, the dopantmaterial easily functions as a hole trap.

For instance, FIG. 4 shows an Ip (ionization potential)-Af (affinity)relationship of the host material and the dopant material in theemitting layer in the above case. In FIG. 4, a shaded area in theemitting layer shows an exciton-density distribution. The same appliesto FIGS. 5 to 7. FIG. 4 shows the relationship in the case ofA_(h)>A_(b)>A_(e).

When a gap in ionization potential between the host material and thedopant material becomes large, the dopant material is likely to have ahole-trapping property, whereby triplet excitons are generated not onlyon the host material molecule but directly on the dopant materialmolecule. Consequently, the triplet excitons generated directly on thedopant material are increased. When a relationship of E^(T) _(h)<E^(T)_(d) is satisfied, triplet exciton energy on the dopant materialmolecule is transferred onto the host molecule by Dexter energytransfer, resulting in that all the triplet excitons gather on the hostmaterial. As a result, The TTF phenomenon occurs efficiently.

In the exemplary embodiment, it is preferred that the hole transportinglayer is adjacent to the emitting layer in the hole transporting zoneand a triplet energy E^(T) _(ho) of the hole transporting layer islarger than a triplet energy E^(T) _(h) of the host material.

When the dopant material has a hole-trapping property, the holesinjected from the hole transporting zone to the emitting layer aretrapped by the dopant material. Accordingly, recombination often occursin the emitting layer near the anode. A typically-known holetransporting material used for the hole transporting zone often exhibitsa larger triplet energy than the host material. Accordingly, diffusionof the triplet excitons on holes-side has not been a problem.

However, even though recombination often occurs near the anode, thetriplet exciton density in the interface of the electron transportingzone cannot be ignored. Even under such conditions, highly efficientrecombination can be achieved by increasing the triplet energy of theblocking layer.

Other factors to determine recombination areas are a carrier mobility,ionization potential, affinity and thickness of each of the holetransporting zone and the electron transporting zone. For instance, whenthe thickness of the hole transporting zone is thicker than that of theelectron transporting zone, an amount of the electrons injected to theemitting layer is relatively decreased. As a result, the recombinationareas are shifted near the electron transporting zone. In such a case,when the blocking layer having a large triplet energy as in theinvention is used, the TTF phenomenon can be efficiently induced.

The host material and the dopant material that satisfy the aboverelationship in the affinity are selected from, for instance, thefollowing compounds (see JP-A-2010-50227 (Japanese Patent ApplicationNo. 2008-212102) and the like).

The host material is an anthracene derivative and a polycyclic aromaticskeleton-containing compound, preferably the anthracene derivative.

The dopant material is at least one compound selected from the groupconsisting of a pyrene derivative, aminoanthracene derivative,aminochrysene derivative and aminopyrene derivative.

Examples of preferable combinations of the host material and the dopantmaterial are the anthracene derivative as the host material and at leastone compound selected from the group consisting of a pyrene derivative,aminoanthracene derivative, aminochrysene derivative and aminopyrenederivative as the dopant material.

The aminoanthracene derivative is specifically exemplified by a compoundrepresented by the following formula (20A).

In the formula (20A), A₁ and A₂ independently represent a substituted orunsubstituted aliphatic hydrocarbon group having 1 to 6 carbon atoms,substituted or unsubstituted aromatic hydrocarbon group having 6 to 20ring carbon atoms, or substituted or unsubstituted heterocyclic aromatichydrocarbon group having 5 to 19 ring atoms and containing nitrogen,sulfur or oxygen atom.

A₃ independently represents a substituted or unsubstituted aliphatichydrocarbon group having 1 to 6 carbon atoms, substituted orunsubstituted aromatic hydrocarbon group having 6 to 20 ring carbonatoms, substituted or unsubstituted heterocyclic aromatic hydrocarbongroup having 5 to 19 ring atoms, or a hydrogen atom. The heterocyclicaromatic hydrocarbon group includes nitrogen, sulfur or oxygen atom.

The aminochrysene derivative is specifically exemplified by a compoundrepresented by the following formula (20B).

In the formula (20B), X₁ to X₁₀ each represent a hydrogen atom or asubstituent. Y₁ and Y₂ each represent a substituent.

X₁ to X₁₀ are preferably a hydrogen atom. Y₁ and Y₂ are preferably asubstituted or unsubstituted aromatic ring having 6 to 30 ring carbonatoms. The substituent of the aromatic ring is preferably an alkyl grouphaving 1 to 6 carbon atoms. The aromatic ring is preferably an aromaticring having 6 to 10 ring carbon atoms or a phenyl group.

The aminopyrene derivative is exemplified by a compound represented bythe following formula (20C).

In the formula (20C), X₁ to X₁₀ each represent a hydrogen atom or asubstituent. X₃ and X₈ or X₂ and X₇ each represent —NY₁Y₂ (Y₁ and Y₂:substituents). When X₃ and X₈ each represent —NY₁Y₂, it is preferredthat X_(2,4,5,7,9,10) represent a hydrogen atom, X₁ and X₆ represent ahydrogen atom, alkyl group or cycloalkyl group. When X₂ and X₇ eachrepresent —NY₁Y₂, it is preferred that X_(1,3-6,8-10) are a hydrogenatom. Y₁ and Y₂ are preferably a substituted or unsubstituted aromaticring, e.g., a phenyl group and a naphthyl group. The substituent of thearomatic ring is exemplified by an alkyl group having 1 to 6 carbonatoms.

The anthracene derivative is preferably a compound represented by theformula (20D).

In the formula (20D), Ar¹¹ and Ar¹² each independently represent asubstituted or unsubstituted monocyclic group having 5 to 30 ring atoms,a substituted or unsubstituted fused cyclic group having 10 to 30 ringatoms or a combination of the monocyclic group and the fused cyclicgroup.

The monocyclic group in the formula (20D) is a group formed only by ringstructure(s) having no fused structure.

The monocyclic group has 5 to 30 ring atoms, preferably 5 to 20 ringatoms. Examples of the monocyclic group include: an aromatic group suchas a phenyl group, biphenyl group, terphenyl group and quarter-phenylgroup; and a heterocyclic group such as a pyridyl group, pyrazyl group,pyrimidyl group, triazinyl group, furyl group and thienyl group. Amongthe monocyclic group, a phenyl group, biphenyl group and terphenyl groupare preferable.

The fused cyclic group in the formula (20D) is a group formed by fusingtwo or more ring structures.

The fused cyclic group has 10 to 30 ring atoms, preferably 10 to 20 ringatoms. Examples of the fused cyclic group include: a fused aromaticcyclic group such as a naphthyl group, phenanthryl group, anthryl group,chrysenyl group, benzoanthryl group, benzophenanthryl group,triphenylenyl group, benzochrysenyl group, indenyl group, fluorenylgroup, 9,9-dimethylfluorenyl group, benzofluorenyl group,dibenzofluorenyl group, fluoranthenyl group and benzofluoranthenylgroup; and a fused heterocyclic group such as a benzofuranyl group,benzothiophenyl group, indolyl group, dibenzofuranyl group,dibenzothiophenyl group, carbazolyl group, quinolyl group andphenanthrolinyl group. Among the fused cyclic group, a naphthyl group,phenanthryl group, anthryl group, 9,9-dimethylfluorenyl group,fluoranthenyl group, benzoanthryl group, dibenzothiophenyl group,dibenzofuranyl group and carbazolyl group are preferable.

The group formed in a combination of the monocyclic group and the fusedcyclic group in the formula (20D) is exemplified by a group combined bysequentially bonding a phenyl group, a naphthyl group and a phenyl groupto an anthracene ring.

Specific examples of the alkyl group, silyl group, alkoxy group, aryloxygroup, aralkyl group and the halogen atom for R¹⁰¹ to R¹⁰⁸ in theformula (20D) are the same as those described in relation to R₁ in theformula (1). Examples of the cycloalkyl group are the same as the aboveexamples of the cycloalkyl group. The same applies to the description of“substituted or unsubstituted” in these substituents.

Preferable examples of the “substituted or unsubstituted” substituentfor Ar¹¹ and Ar¹² and R¹⁰¹ to R¹⁰⁸ in the formula (20D) are a monocyclicgroup, fused cyclic group, alkyl group, cycloalkyl group, silyl group,alkoxy group, cyano group and halogen atom (particularly, fluorine). Themonocyclic group and the fused cyclic group are particularly preferable.Preferable specific examples of the substituents are the same as theabove examples of the groups in the formula (20D) and the above examplesof the groups in the formula (1).

[2] Case of A_(h)<A_(d)

Using the combination of the host material and the dopant material whichallows A_(h)<A_(d), the advantageous effects of the blocking layerprovided within the electron transporting zone is exhibitedoutstandingly, whereby improvement in efficiency due to the TTFphenomenon can be attained. Description will be given in the followingcases of [2-1] and [2-2]. In general, an organic material has abroadening of a LUMO level in a range larger than the measured affinitylevel by approximately 0.2 eV.

[2-1] Difference Between A_(d) and A_(h) is Smaller than 0.2 eV

FIG. 5 shows one example of an energy band diagram in this case. Dottedlines in the emitting layer show an energy level of the dopant material.As shown in FIG. 5, when a difference between A_(d) and A_(h) is smallerthan 0.2 eV, the LUMO level of the dopant material is included in therange of the broadening of the LUMO level of the host material, so thatthe electrons carried within the emitting layer is less likely to betrapped by the dopant material. In other words, the dopant material isless likely to exhibit an electron-trapping property. Moreover, thedopant material in the exemplary embodiment is a wide-gap fluorescentdopant material having a main peak wavelength of 550 nm or less. Whenthe relationship of A_(h)<A_(d) is satisfied, since the differencebetween A_(h) and A_(d) is approximately 0.2 eV, a difference betweenthe ionization potential of the host material and the ionizationpotential of the dopant material is reduced. As a result, the dopantmaterial does not tend to exhibit an outstanding hole-trapping property.FIG. 5 shows the relationship in the case of A_(h)>A_(b)>A_(e).

In other words, the dopant material in this case does not tend toexhibit an outstanding trapping property for both electrons and holes.In this case, as shown by the shaded area of the emitting layer in FIG.5, the electron-hole recombination occur mainly on the host materialmolecule in the broad whole area in the emitting layer, therebygenerating 25% of singlet excitons and 75% of triplet excitons mainly onthe host material molecule. Energy of the singlet excitons generated onthe host material is transferred to the dopant material by Forsterenergy transfer to contribute to a fluorescent emission of the dopantmaterial molecule. On the other hand, the transfer direction of theenergy of triplet excitons depends on the triplet energy relationship ofthe host material and the dopant material. When the relationship isE^(T) _(h)>E^(T) _(d), the triplet excitons generated on the hostmaterial are transferred to a dopant material which exists in thevicinity by the Dexter energy transfer. A concentration of the dopantmaterial in the emitting layer of a fluorescent device is typically aslow as at a few mass % to approximately 20 mass %. Accordingly, tripletexcitons which have transferred to the dopant material collide with oneanother less frequently, resulting in a less possibility of occurrenceof the TTF phenomenon. However, when the relationship of E^(T)_(h)<E^(T) _(d) is satisfied as in this exemplary embodiment, since thetriplet excitons are present on the host material molecule, thefrequency of collision is increased, so that the TTF phenomenon easilyand efficiently occur.

In the exemplary embodiment, the blocking layer is adjacent to theemitting layer. Since the triplet energy E^(T) _(b) of the blockinglayer is set to be larger than the triplet energy E^(T) _(h) of the hostmaterial, the triplet excitons is prevented from dispersing in theelectron transporting zone, so that the TTF phenomenon can occurefficiently in the emitting layer.

[2-2] Difference Between A_(d) and A_(h) is Larger than 0.2 eV

FIG. 6 shows one example of an energy band diagram in this case. Thedifference in affinity between the dopant material and the host materialis increased, so that a LUMO level of the dopant material is present ata position further higher than the LUMO level broadening of the hostmaterial. Accordingly, the dopant material is more likely to exhibit asignificant electron-trapping property. Electrons trapped by the dopantmaterial are recombined with holes after the holes are transferred fromthe host material to the dopant material. In other words, unlike thecondition shown in FIG. 5, the electrons and the holes are recombined ina pair not only on the host material molecule but also on the dopantmaterial molecule. As a result, triplet excitons are generated not onlyon the host material molecule but also directly on the dopant materialmolecule. Under such conditions, when the relationship of E^(T)_(h)<E^(T) _(d) is satisfied as in this exemplary embodiment, thetriplet excitons generated directly on the dopant material also gatheron the host material by Dexter energy transfer, so that the TTFphenomenon occurs efficiently.

When the affinities satisfy the above-mentioned relationship, thepossibility of trapping of electrons by the dopant material is increasedtoward the interface between the emitting layer and the blocking layer.As a result, recombination occurs frequently in the vicinity of theinterface between the emitting layer and the blocking layer. In thiscase, the efficiency of confining triplet excitons by the blocking layeris increased as compared with the case mentioned in [2-1], resulting inan increase in density of triplet excitons at the interface between theemitting layer and the blocking layer. FIG. 6 shows the relationship inthe case of A_(h)>A_(b)>A_(e).

The host material and the dopant material that satisfy the aboverelationship in the A_(h)<A_(d) can be selected from, for instance, thefollowing compounds (see JP-A-2010-50227 (Japanese Patent ApplicationNo. 2008-212102) and the like).

Examples of the host material are an anthracene derivative and apolycyclic aromatic skeleton-containing compound, preferably ananthracene derivative.

Examples of the dopant material are a fluoranthene derivative, pyrenederivative, arylacetylene derivative, fluorene derivative, boroncomplex, perylene derivative, oxadiazole derivative and anthracenederivatives, preferably fluoranthene derivative, pyrene derivative, andboron complex, more preferably fluoranthene derivative and boroncomplex. As for the combination of the host material and the dopantmaterial, it is preferred that the host material is an anthracenederivative and the dopant material is a fluoranthene derivative or aboron complex.

The fluoranthene derivative is exemplified by the following compound.

In the formula (30A), X₁ to X₁₂ each represent a hydrogen atom or asubstituent. Preferably, in the compound, X₁ to X₂, X₄ to X₆ and X₈ toX₁₁ are a hydrogen atom, and X₃, X₇ and X₁₂ are a substituted orunsubstituted aryl group having 5 to 50 ring atoms. Preferably, in thecompound, X₁ to X₂, X₄ to X₆ and X₈ to X₁₁ are a hydrogen atom, X₃, X₇and X₁₂ are a substituted or unsubstituted aryl group having 5 to 50ring atoms. X₃ is —Ar₁—Ar₂, in which Ar₁ is a substituted orunsubstituted arylene group having 5 to 50 ring atoms, and Ar₂ is asubstituted or unsubstituted aryl group having 5 to 50 ring atoms.

More preferably, in the compound, X₁ to X₂, X₄ to X₆ and X₈ to X₁₁ are ahydrogen atom and X₇ and X₁₂ are a substituted or unsubstituted arylgroup having 5 to 50 ring atoms. X₃ is —Ar₁—Ar₂—Ar₃, in which Ar₁ andAr₃ are each a substituted or unsubstituted arylene group having 5 to 50ring atoms, and Ar₂ is a substituted or unsubstituted aryl group having5 to 50 ring atoms.

The boron complex is exemplified by the following compound.

In the formula (30B), A and A′ represent an independent azine ringsystem corresponding to a six-membered aromatic ring containing one ormore nitrogen. X^(a) and X^(b) represent independently-selectedsubstituents, which are bonded together to form a fused ring for thering A or the ring A′. The fused ring contains an aryl or heteroarylsubstituent. m and n independently represent 0 to 4. Z^(a) and Z^(b)each represent an independently-selected halide. 1, 2, 3, 4, 1′, 2′, 3′and 4′ each represent an independently-selected carbon atom or nitrogenatom.

Desirably, the azine ring is preferably a quinolinyl ring orisoquinolinyl ring in which all of 1, 2, 3, 4, 1′, 2′, 3′ and 4′ arecarbon atoms, m and n each are 2 or more, and X^(a) and X^(b) are asubstituent having 2 or more carbon atoms that combine with each otherto form an aromatic ring. Z^(a) and Z^(b) are desirably fluorine atoms.

The anthracene derivatives as the host material in the case of [2] arethe same as those described in the above “[1] Case of A_(h)>A_(d).”

[3] Case where a Dopant Material Satisfying A_(h)<A_(d) and a DopantMaterial Satisfying A_(h)>A_(d) Coexist

FIG. 7 shows one example of an energy band diagram when a dopantmaterial satisfying A_(h)<A_(d) and a dopant material satisfyingA_(h)>A_(d) are both contained in the emitting layer. In such a case,both electrons and holes are trapped properly, whereby recombinationoccurs in the entire region of the emitting layer. Accordingly,recombination occurs frequently also on the cathode side. By providing ablocking layer that has a large triplet energy, the TTF phenomenonoccurs efficiently. FIG. 7 shows the relationship in the case ofA_(h)>A_(b)>A_(e).

In the exemplary embodiment, the density of excitons is large in theinterface between the emitting layer and the blocking layer. In thiscase, holes which do not contribute to recombination in the emittinglayer are injected in the blocking layer with a high probability.Accordingly, among the above-mentioned aromatic heterocyclicderivatives, one having an excellent oxidation resistance is preferableas the material to be used in the blocking layer.

The blocking layer material desirably exhibits a reversible oxidationprocess in a cyclic voltammetry measurement.

The emitting layer may contain two or more fluorescent dopant materialsof which the main peak wavelength is 550 nm or less. When the emittinglayer contains two or more fluorescent dopant materials, the affinityA_(d) of at least one dopant material is equal to or larger than theaffinity A_(h) of the host material, and the triplet energy E^(T) _(d)of this dopant material is larger than the triplet energy E^(T) _(h) ofthe host material. For instance, the affinity A_(d) of at least onedopant material of the rest of the dopant materials may be smaller thanthe affinity A_(h) of the host material. Containing such two kinds ofdopant materials means containing both of a dopant material satisfyingA_(h)<A_(d) and a dopant material satisfying A_(h)>A_(d) as describedabove. Efficiency can be significantly improved by providing theblocking layer having a large triplet energy.

Examples of the dopant material having the affinity A_(d) that issmaller than the affinity A_(h) of the host material include a pyrenederivative, aminoanthracene derivative, aminochrysene derivative, andaminopyrene derivative.

In addition to the above-mentioned host materials, dibenzofurancompounds disclosed in WO05/113531 and JP2005-314239, fluorene compoundsdisclosed in WO02/14244, and benzanthracene compounds disclosed inWO08/145,239 can be used.

In addition to the above-mentioned dopant materials, pyrene compoundsdisclosed in JP2004-204238, WO05/108348, WO04/83162, WO09/84512,KR10-2008-79956, KR10-2007-115588 and KR10-2010-24894, chrysenecompounds disclosed in WO04/44088, and anthracene compounds disclosed inWO07/21117 can be used.

Preferably, the host material and the dopant material are each acompound formed by bonding ring structures or single atoms (includingbonding of a ring structure and a single atom), in which the bonding isa single bond. A compound having a carbon-carbon double bond in the partother than the ring structure thereof is not preferable The reasonthereof is that the triplet energies generated on the host material andthe dopant material are used for the structural change of the doublebond, not for a TTF phenomenon.

Formation Method of Each Layer of Organic EL Device

Each layer of the organic EL device in the exemplary embodiment may beformed by any one of dry film-forming such as vacuum deposition,sputtering, plasma deposition and ion plating, and wet film-forming suchas spin coating, dipping, flow coating and ink jet.

In the wet film-forming, materials for forming each layer are dissolvedor dispersed in an appropriate solvent such as ethanol, chloroform,tetrahydrofuran and dioxane to form a thin-film. Any one of the solventsis usable.

As a solution suitable for the wet film-forming, anorganic-EL-material-containing solution, which contains an aromaticamine derivative of the invention as an organic-EL-device material and asolvent, is usable.

In any one of the organic thin-film layer, a resin or an additivesuitable for improving film-forming performance and preventing pin holeson a film may be used.

Thickness of Each Layer of Organic EL Device

Although a thickness is not limited, an appropriate thickness needs tobe set. When the thickness is excessively thick, a large voltage isrequired to be applied in order to obtain a predetermined emission, sothat an efficiency is deteriorated. When the thickness is excessivelythin, pin holes or the like generate. Accordingly, even when theelectrical field is applied to the film, a sufficient luminescenceintensity is not obtained. A thickness of the blocking layer ispreferably 20 nm or less. A thickness of each of other layers istypically preferably in a range of 5 nm to 10 μm, more preferably in arange of 10 nm to 0.2 μm.

Second Exemplary Embodiment

FIG. 8 shows one example of an organic EL device 2 according to a secondexemplary embodiment.

The organic EL device according to the second exemplary embodiment maynot include an electron injecting layer. As shown in FIG. 8, the organicEL device 2 according to the second exemplary embodiment includes theanode 10, the hole transporting zone 60, the emitting layer 20, theelectron transporting zone (the blocking layer 30 in the exemplaryembodiment), and the cathode 50 in this sequence. These layers areadjacent to one another in the organic EL device in the exemplaryembodiment.

The blocking layer 30 of the organic EL device 2 contains the aromaticheterocyclic derivative represented by the formula (1) in the samemanner as in the first exemplary embodiment. Other layers forming theorganic EL device 2 are also the same as those in the first exemplaryembodiment.

Third Exemplary Embodiment

FIG. 9 shows one example of an organic EL device 3 according to a thirdexemplary embodiment.

The organic EL device according to the third exemplary embodiment mayinclude an electron injecting layer on a side of the electrontransporting layer near the cathode. As shown in FIG. 9, the organic ELdevice 3 according to the third exemplary embodiment includes the anode10, the hole transporting zone 60, the emitting layer 20, the electrontransporting zone (the blocking layer 30, the electron transportinglayer 41 and the electron injecting layer 40 in the exemplaryembodiment), and the cathode 50 in this sequence. These layers areadjacent to one another in the exemplary embodiment.

In the organic EL device 3, at least one of the electron injecting layer40 and the electron transporting layer 41 preferably contains thearomatic heterocyclic derivative according to the above exemplaryembodiment. A material to be contained in the electron transportinglayer can be the material described in relation to the above electroninjecting layer and known electron transporting materials. Moreover, theelectron injecting layer 40 and the electron transporting layer 41 mayfurther include other material(s) in addition to the aromaticheterocyclic derivative according to the above exemplary embodiment.

The blocking layer 30 of the organic EL device 3 contains the aromaticheterocyclic derivative represented by the formula (1) in the samemanner as in the first exemplary embodiment. Other layers forming theorganic EL device 3 are also the same as those in the first exemplaryembodiment.

Fourth Exemplary Embodiment

An organic EL device in the fourth exemplary embodiment may have atandem device configuration in which at least two organic layer unitsincluding emitting layers are provided. An intermediate layer(intermediate conductive layer, charge generation layer or CGL) isinterposed between the two emitting layers. An electron transportingzone can be provided in each unit. At least one emitting layer is afluorescent emitting layer and the unit including the emitting layersatisfies the above-mentioned requirements.

FIG. 10 shows one example of the organic EL device according to thefourth exemplary embodiment. An organic EL device 4 includes the anode10, emitting layers 22 and 24 and the cathode 50 in this sequence. Anintermediate layer 80 is interposed between the emitting layers 22 and24. A blocking layer 32 is adjacent to the emitting layer 24. Theelectron injecting layer 40 is interposed between the blocking layer 32and the cathode 50. The blocking layer 32, the electron injecting layer40 and the emitting layer 24 are respectively a blocking layer, anelectron injecting layer and a fluorescent emitting layer which satisfythe requirements of the invention. The other emitting layer may beeither a fluorescent emitting layer or a phosphorescent emitting layer.Another blocking layer and another electron injecting layer are providedadjacent to the emitting layer 22 in sequential order. These blockinglayer and electron injecting layer and the emitting layer 22 may berespectively used as the blocking layer, the electron injecting layer,and the fluorescent emitting layer which satisfy the requirements of theinvention.

Note that, in the exemplary embodiment, the blocking layer 32 and theelectron injecting layer 40 correspond to the electron transportingzone.

At least one of an electron transporting zone and hole transporting zonemay be interposed between the two emitting layers 22 and 24. Three ormore emitting layers may be provided, and two or more intermediatelayers may be provided. When three or more emitting layers are present,an intermediate layer may or may not be present between all of theemitting layers.

The intermediate layer is a layer including at least one of theintermediate conductive layer and the charge generation layer, or atleast one of the intermediate conductive layer and the charge generationlayer. The intermediate layer serves as a source for supplying electronsor holes to be injected in an emitting unit. In addition to chargesinjected from a pair of electrodes, charges supplied from theintermediate layer are injected into the emitting unit. Accordingly, byproviding the intermediate layer, luminous efficiency (currentefficiency) relative to injected current is improved.

Examples of the intermediate layer include a metal, metal oxide, mixtureof metal oxides, composite oxide, and electron-accepting organiccompound. Examples of the metal are preferably Mg, Al, and a film formedby co-evaporating Mg and Al. Examples of the metal oxide include ZnO,WO₃, MoO₃ and MoO₂. Examples of the mixture of the metal oxides includeITO, IZO (registered trade mark), and ZnO:Al. Examples of theelectron-accepting organic compound include an organic compound having aCN group as a substituent. The organic compound having a CN group ispreferably a triphenylene derivative, tetracyanoquinodimethanederivative and indenofluorene derivative. The triphenylene derivative ispreferably hexacyanohexaazatriphenylene. The tetracyanoquinodimethanederivative is preferably tetrafluoroquinodimethane anddicyanoquinodimethane. The indenofluorene derivative is preferably acompound disclosed in WO2009/011327, WO2009/069717, or WO2010/064655.The electron accepting substance may be a single substance, or a mixturewith other organic compounds.

In order to easily accept the electrons from the charge generationlayer, at least one of the electron-donating dopant represented by analkali metal and the organic metal complex is added in the vicinity ofthe interface of the charge generation layer in the electrontransporting layer. Examples of the electron-donating dopant and theorganic metal complex are those described above in the first exemplaryembodiment.

Specific examples of the compounds usable for the electron-donatingdopant and the organic metal complex are compounds disclosed inInternational Patent Application No. PCT/JP2010/003434 (InternationalPublication No. WO2010/134352).

Fifth Exemplary Embodiment

In the fifth exemplary embodiment, an anode, a plurality of emittinglayers, an electron transporting zone that includes a blocking layeradjacent to one of the emitting layers and an electron injecting layeradjacent to the blocking layer, and a cathode are provided in sequentialorder. A charge blocking layer is provided between two emitting layersof the plurality of the emitting layers. The emitting layers in contactwith the charge blocking layer are fluorescent emitting layers. Thefluorescent emitting layer, and the blocking layer and the electroninjecting layer in the electron transporting zone satisfy the aboverequirements.

As a configuration of a suitable organic EL device according to thefifth exemplary embodiment, there can be given a configuration asdisclosed in Japanese Patent No. 4134280, US patent publicationUS2007/0273270A1 and International Publication WO2008/023623A1.Specifically, the configuration in which an anode, a first emittinglayer, a charge blocking layer, a second emitting layer and a cathodeare sequentially stacked, and an electron-transporting zone having ablocking layer and an electron injecting layer for preventing diffusionof triplet excitons is further provided between the second emittinglayer and the cathode. Here, the charge blocking layer means a layer tocontrol the carrier injection to an emitting layer and the carrierbalance between electrons and holes injected in the emitting layer byproviding an energy barrier of a HOMO level or a LUMO level betweenadjacent emitting layers

Specific examples of such a configuration are given below.

anode/first emitting layer/charge blocking layer/second emittinglayer/electron transporting zone/cathode

anode/first emitting layer/charge blocking layer/second emittinglayer/third emitting layer/electron transporting zone/cathode

It is preferred that a hole transporting zone is provided between theanode and the first emitting layer in the same manner as in otherembodiments

FIG. 11 shows one example of an organic EL device according to the fifthexemplary embodiment. An upper view in FIG. 11 shows a deviceconfiguration, and the HOMO and LUMO energy levels of each layer. Alower view in FIG. 11 shows a relationship between energy gaps of thethird emitting layer and the blocking layer. The upper view in FIG. 11shows the relationship in the case of A_(h)>A_(b)>A_(e).

The organic EL device includes the anode, first emitting layer, secondemitting layer, third emitting layer, electron transporting zone, andcathode in sequential order. A charge blocking layer is interposedbetween the first and second emitting layers. The electron transportingzone is formed of the blocking layer. This blocking layer and thirdemitting layer are the blocking layer and the fluorescent emitting layerthat satisfy the requirements of the invention. The first and secondemitting layers may be either a fluorescent emitting layer or aphosphorescent emitting layer.

The device of this embodiment is suitable as a white emitting device.The device can be a white emitting device by adjusting the emissioncolors of the first emitting layer, second emitting layer and thirdemitting layer. Moreover, the device can be a white emitting device byarranging only the first emitting layer and the second emitting layerand adjusting the emission colors of these two emitting layers. In thiscase, the second emitting layer is a fluorescent emitting layersatisfying the requirements of the invention.

In particular, by using a hole transporting material as the host in thefirst emitting layer, by adding a fluorescent dopant material of whichthe main peak wavelength is larger than 550 nm, by using an electrontransporting material as the host material in the second emitting layer(and the third emitting layer), and by adding a fluorescent dopantmaterial of which the main peak wavelength is equal to or smaller than550 nm, it is possible to achieve a white emitting device that exhibitsa higher luminous efficiency as compared with conventional whiteemitting devices, even though all of them are entirely formed offluorescent materials.

Reference is made particularly to a hole transporting layer which isadjacent to the emitting layer. In order to allow the TTF phenomenon tooccur effectively, it is preferred that the triplet energy of the holetransporting material is larger than the triplet energy of the hostmaterial, when the triplet energy of the hole transporting material andthat of the host material are compared.

Sixth Exemplary Embodiment

In a sixth exemplary embodiment, a blue pixel, a green pixel and a redpixel are arranged in parallel on a substrate. Of these three colorpixels, at least one of the blue pixel and the green pixel has theconfiguration of the first exemplary embodiment or second exemplaryembodiment.

FIG. 12 shows one example of an organic EL device according to the fifthexemplary embodiment.

In a top-emission type organic EL device 5 shown in FIG. 12, a bluepixel B, a green pixel G and a red pixel R are arranged in parallel on acommon substrate 100.

The blue pixel B includes the anode 10, the hole transporting zone 60, ablue emitting layer 20B, the blocking layer 32, the electron injectinglayer 40, the cathode 50, and a protection layer 90 on the substrate 100in sequential order.

The green pixel G includes the anode 10, the hole transporting zone 60,a green emitting layer 20G, the blocking layer 32, the electroninjecting layer 40, the cathode 50, and the protection layer 90 on thesubstrate 100 in sequential order.

The red pixel R includes the anode 10, the hole transporting zone 60, ared emitting layer 20R, the blocking layer 32, the electron injectinglayer 40, the cathode 50, and the protection layer 90 on the substrate100 in sequential order.

An insulating film 200 is formed between the anodes of adjacent pixelsso as to keep the insulation between the pixels. The electrontransporting zone is formed of the blocking layer 32 and the electroninjecting layer 40.

In the organic EL device 5, the blocking layer is provided as a commonblocking layer for the blue pixel B, the red pixel R and the green pixelG.

The advantageous effects brought by the blocking layer are outstandingcomparing to the luminous efficiency conventionally attained in a bluefluorescent device. In a green fluorescent device and a red fluorescentdevice, similar advantageous effects, such as confining triplet energiesin the emitting layer, can be attained, and improvement in luminousefficiency can also be expected.

On the other hand, in a phosphorescent emitting layer, it is possible toattain the advantageous effects of confining triplet energies in theemitting layer, and as a result, diffusion of triplet energies isprevented, thereby contributing to improvement in luminous efficiency ofa phosphorescent dopant material.

The hole transporting zone is formed of, for instance, a holetransporting layer, or a combination of a hole transporting layer and ahole injecting layer. A common hole transporting zone may be provided ordifferent hole transporting zones may be provided for the blue pixel B,the red pixel R and the green pixel G. Typically, the hole transportingzones respectively have a configuration suited to the color of emittedlight.

The configuration of the organic layer formed of the emitting layers20B, G and R and the blocking layer is not limited to that shown in thefigure and is changeable appropriately.

The host material and the dopant material usable in the exemplaryembodiment are the same as described above. In particular, emittinglayers for each color will be described below.

A green emitting layer is preferably formed of the following hostmaterial and dopant material.

The host material is preferably a fused aromatic ring derivative. As thefused aromatic ring derivative, an anthracene derivative, pyrenederivative and the like are more preferable in view of luminousefficiency and luminous lifetime.

The host material is exemplified by a heterocycle-containing compound.Examples of the heterocycle-containing compound are a carbazolederivative, dibenzofuran derivative, ladder-type furan compound andpyrimidine derivative.

The dopant material is not particularly limited so long as it functionsas a dopant, but an aromatic amine derivative is preferable in view ofluminous efficiency and the like. As the aromatic amine derivative, afused aromatic ring derivative having a substituted or unsubstitutedarylamino group is preferable. Examples of such a compound are pyrene,anthracene and chrysene having an arylamino group.

A styrylamine compound is also preferable as the dopant material.Examples of the styrylamine compound are styrylamine, styryldiamine,styryltriamine and styryltetraamine. Here, the styrylamine means acompound in which a substituted or unsubstituted arylamine issubstituted with at least one arylvinyl group. The arylvinyl group maybe substituted with a substituent such as an aryl group, silyl group,alkyl group, cycloalkyl group, or arylamino group, which may have afurther substituent.

Furthermore, as the dopant material, a boron complex and a fluoranthenecompound are preferable. A metal complex is also preferable as thedopant material. The metal complex is exemplified by an iridium complexor platinum complex.

A red emitting layer is preferably formed of the following host materialand dopant material. The host material is preferably a fused aromaticring derivative. As the fused aromatic ring derivative, a naphthacenederivative, pentacene derivative and the like are more preferable inview of luminous efficiency and luminous lifetime.

The host material is exemplified by a fused polycyclic aromaticcompound. Examples of the fused polycyclic aromatic compound are anaphthalene compound, phenanthrene compound and fluoranthene compound.

The dopant material is preferably an aromatic amine derivative. As thearomatic amine derivative, a fused aromatic ring derivative having asubstituted or unsubstituted arylamino group is preferable. Such acompound is exemplified by periflanthene having an arylamino group.

A metal complex is also preferable as the dopant material. The metalcomplex is exemplified by an iridium complex or platinum complex.

The organic EL device of the sixth exemplary embodiment is prepared inthe following manner.

On a substrate, an APC (Ag—Pd—Cu) layer as a silver alloy layer(reflective layer) and a transparent conductive layer such as a zincoxide (IZO) film and a tin oxide film are sequentially formed. Next, bya typical lithographic technology, this conductive material layer ispatterned by etching using a mask with a resist pattern, thereby formingan anode. Then, by the spin coating method, an insulating film formed ofa photosensitive resin such as a polyimide is formed by coating on theanode. Thereafter, the resulting film is exposed, developed and cured toallow the anode to be exposed, whereby the anodes for a blue emittingregion, a green emitting region and a red emitting region are patterned.

There are three types of electrodes, i.e. an electrode for the redpixel, an electrode for the green pixel and an electrode for a bluepixel. They respectively correspond to the blue emitting region, thegreen emitting region and the red emitting region, and respectivelycorrespond to the anode. After conducting cleaning for 5 minutes inisopropyl alcohol, a UV ozone cleaning is conducted for 30 minutes. Whenthe hole injecting layer and the hole transporting layer are formedthereafter, the hole injecting layer is stacked over the entire surfaceof the substrate, and the hole transporting layer is stacked thereon.Emitting layers are formed to be correspondingly arranged to thepositions of the anode for the red pixel, the anode for the green pixeland the anode for the blue pixel When vacuum evaporation method is used,the blue emitting layer, the green emitting layer and the red emittinglayer are finely patterned using a shadow mask.

Next, a blocking layer is stacked over the entire surface. Subsequently,an electron injecting layer is stacked over the entire surface.Thereafter, Mg and Ag are formed into a film by evaporation, therebyforming a semi-transparent cathode formed of an Mg—Ag alloy.

As for the other members used in the exemplary embodiment, such as thesubstrate, the anode, the cathode, the hole injecting layer and the holetransporting layer, known members disclosed in PCT/JP2009/053247,PCT/JP2008/073180, U.S. patent application Ser. No. 12/376,236, U.S.patent application Ser. No. 11/766,281, U.S. patent application Ser. No.12/280,364 or the like can be appropriately selected and used.

It is preferred that the hole transporting layer include an aromaticamine derivative represented by any one of the following formulae (a-1)to (a-5).

In the formulae (a-1) to (a-5), Ar₁ to Ar₂₄ are independently asubstituted or unsubstituted aryl group having 6 to 50 ring carbonatoms, or a substituted or unsubstituted heteroaryl group having 5 to 50ring atoms.

L₁ to L₉ are independently a substituted or unsubstituted arylene grouphaving 6 to 50 ring carbon atoms or a substituted or unsubstitutedheteroarylene group having 5 to 50 ring atoms.

Examples of a substituent which Ar₁ to Ar₂₄ and L₁ to L₉ may haveinclude a linear or branched alkyl group having 1 to 15 carbon atoms, acycloalkyl group having 3 to 15 ring carbon atoms, a trialkylsilyl grouphaving a linear or branched alkyl group having 1 to 15 carbon atoms, atriarylsilyl group having an aryl group having 6 to 14 ring carbonatoms, an alkylarylsilyl group having a linear or branched alkyl grouphaving 1 to 15 carbon atoms and an aryl group having 6 to 14 ring carbonatoms, an aryl group having 6 to 50 ring carbon atoms, a heteroarylgroup having 5 to 50 ring atoms, a halogen atom, and a cyano group.Adjacent substituents may bond to each other to form a saturated orunsaturated divalent group forming a ring.

At least one of the above Ar₁ to Ar₂₄ is preferably a substituentrepresented by the following formula (a-6) or (a-7).

In the formula (a-6), X is an oxygen atom, sulfur atom or N—Ra. Ra is alinear or branched alkyl group having 1 to 15 carbon atoms, a cycloalkylgroup having 3 to 15 ring carbon atoms, an aryl group having 6 to 50ring carbon atoms or a heteroaryl group having 5 to 50 ring atoms.

L₁₀ is a single bond, a substituted or unsubstituted arylene grouphaving 6 to 50 ring carbon atoms, or a substituted or unsubstitutedheteroarylene group having 5 to 50 ring atoms.

In the formula (a-7), L₁₁ is a substituted or unsubstituted arylenegroup having 6 to 50 ring carbon atoms, or a substituted orunsubstituted heteroarylene group having 5 to 50 ring atoms.

In the formulae (a-6) and (a-7), R¹ to R⁴ are independently a linear orbranched alkyl group having 1 to 15 carbon atoms, a cycloalkyl grouphaving 3 to 15 ring carbon atoms, a trialkylsilyl group having a linearor branched alkyl group having 1 to 15 carbon atoms, a triarylsilylgroup having an aryl group having 6 to 14 ring carbon atoms, analkylarylsilyl group having a linear or branched alkyl group having 1 to15 carbon atoms and an aryl group having 6 to 14 ring carbon atoms, anaryl group having 6 to 14 ring carbon atoms, a heteroaryl group having 5to 50 ring atoms, a halogen atom, or a cyano group. Adjacent groups ofR¹s to R⁴ s may bond to each other to form a ring.

a, c and d are each an integer of 0 to 4.

b is an integer of 0 to 3.

The compound represented by the formula (a-1) is preferably a compoundrepresented by the following formula (a-8).

In the formula (a-8), Cz is a substituted or unsubstituted carbazolylgroup.

L₁₂ is a substituted or unsubstituted arylene group having 6 to 50 ringcarbon atoms, or a substituted or unsubstituted heteroarylene grouphaving 5 to 50 ring atoms.

Ar₂₅ and Ar₂₆ are independently a substituted or unsubstituted arylgroup having 6 to 50 ring carbon atoms or a substituted or unsubstitutedheteroaryl group having 5 to 50 ring atoms.

The compound represented by the formula (a-8) is preferably a compoundrepresented by the following formula (a-9).

In the formula (a-9), R⁵ and R⁶ are independently a linear or branchedalkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to15 ring carbon atoms, a trialkylsilyl group having a linear or branchedalkyl group having 1 to 15 carbon atoms, a triarylsilyl group having anaryl group having 6 to 14 ring carbon atoms, an alkylarylsilyl grouphaving a linear or branched alkyl group having 1 to 15 carbon atoms andan aryl group having 6 to 14 ring carbon atoms, an aryl group having 6to 14 ring carbon atoms, a heteroaryl group having 5 to 50 ring atoms, ahalogen atom, or a cyano group. Adjacent groups of R⁵ s to R⁶ s may bondto each other to form a ring.

e and f are each an integer of 0 to 4.

L₁₂, Ar₂₅ and Ar₂₆ are the same as L₁₂, Ar₂₅ and Ar₂₆ in the formula(a-8).

The compound represented by the formula (a-9) is preferably a compoundrepresented by the following formula (a-10).

In the formula (a-10), R⁷ and R⁸ are independently a linear or branchedalkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to15 ring carbon atoms, a trialkylsilyl group having a linear or branchedalkyl group having 1 to 15 carbon atoms, a triarylsilyl group having anaryl group having 6 to 14 ring carbon atoms, an alkylarylsilyl grouphaving a linear or branched alkyl group having 1 to 15 carbon atoms andan aryl group having 6 to 14 ring carbon atoms, an aryl group having 6to 14 ring carbon atoms, a heteroaryl group having 5 to 50 ring atoms, ahalogen atom, or a cyano group. Adjacent groups of R⁵s to R⁶s may bondto each other to form a ring.

g and h are each an integer of 0 to 4.

R⁵, R⁶, e, f, Ar₂₅ and Ar₂₆ are the same as R⁵, R⁶, e, f, Ar₂₅ and Ar₂₆in the formula (a-9).

Seventh Exemplary Embodiment

An organic EL device according to the seventh exemplary embodiment mayinclude the electron transporting layer in place of the blocking layer30 as the electron transporting zone in the organic EL device 2according to the second exemplary embodiment in FIG. 8. Specifically,the organic EL device according to the seventh exemplary embodiment (notshown) include the anode 10, the hole transporting zone 60, the emittinglayer 20, the electron transporting layer and the cathode 50 in thissequence. The electron transporting layer includes the aromaticheterocyclic derivative of the invention and may further include othermaterial(s). In the seventh exemplary embodiment, the emitting layer 20preferably contains a dopant material exhibiting phosphorescence as thedopant material.

Note that other layers forming the organic EL device in the seventhexemplary embodiment are the same as those in the first and secondexemplary embodiments.

EXAMPLES

Examples of the invention will be described below. However, theinvention is not limited by these Examples.

Synthesis of Compound(s) Synthesis Example 1: Synthesis of Compound 7

A synthesis scheme of a compound 7 is shown below.

(1-1) Synthesis of Compound 3

4′-bromoacetophenone (a compound 1) (22 g, 120 mmol),4-phenylbenzaldehyde (a compound 2) (25 g, 126 mmol), sodium methoxide(8.4 g, 156 mmol) and ethanol (200 mL) were mixed and stirred for 12hours at the room temperature. A precipitated solid was separated byfiltration and suspended in and washed with ethanol. Subsequently, theobtained solid was dried under reduced pressure, so that a compound 3(42 g, a yield of 96%) in a form of a white solid was obtained.

(1-2) Synthesis of Compound 5

Ethanol (450 mL) was added with the compound 3 (40 g, 111 mmol),benzamidine hydrochloride (a compound 4) (26 g, 166 mmol) and sodiumhydroxide (12 g, 299 mmol), and was heated to reflux for nine hours.After the reaction, a precipitated solid was separated by filtration andrefined by silica-gel column chromatography (eluent: toluene). Thereactant was recrystallized using toluene, so that a compound 5 in aform of a white solid (24 g, a yield of 47%) was obtained.

(1-3) Synthesis of Compound 7

The compound 5 (6.0 g, 13 mmol) and a compound 6 (3.3 g, 16 mmol) weredissolved in toluene (200 mL) and 1,2-dimethoxyethane (200 mL), to whichtetrakis(triphenylphosphine)palladium (0) (0.75 g, 0.65 mmol) and anaqueous solution of 2M sodium carbonate (26 mL) were added. The obtainedsolution was heated to reflux for 15 hours. After the reaction, thereactant solution was cooled to the room temperature and extracted withtoluene. The obtained organic layer was washed with water and saturatedsaline in sequential order and dried with sodium sulfate. The solventwas distilled away under reduced pressure. The residue was added withtoluene and heated to reflux to be dissolved. The reactant solution wascooled and precipitated in a crystal form. The crystal was separated byfiltration and washed with toluene. Subsequently, the obtained solid wasdried under reduced pressure, so that a compound 7 (5.5 g, a yield of77%) in a form of a white solid was obtained. As a result of FD-MS(Field Desorption Mass Spectrometry) analysis, the reactant wasidentified as the compound 7.

Synthesis Example 2: Synthesis of Compound 9

A synthesis scheme of a compound 9 is shown below.

(2-1) Synthesis of Compound 9

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using a compound 8 (2.7 g, 13 mmol) in place ofthe compound 6, so that a compound 9 (5.5 g, a yield of 92%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound9.

Synthesis Example 3: Synthesis of Compound 13

A synthesis scheme of a compound 13 is shown below.

(3-1) Synthesis of Compound 12

4′-(p-bromophenyl)acetophenone (a compound 10) (30 g, 110 mmol) andbenzaldehyde (12 g, 110 mmol) were dissolved in ethanol (300 mL), intowhich sodium methoxide (about-5M methanol solution) (80 mL) was dropped.The obtained solution was stirred for three hours at the roomtemperature to synthesize a compound 11. Next, benzamidine hydrochloride(the compound 4) (17 g, 110 mmol) and sodium hydroxide (5.3 g, 132 mmol)were added to the above solution and was heated to reflux for 18 hours.After the reaction, the reactant solution was cooled to the roomtemperature and a precipitated solid was separated by filtration. Then,the obtained solid was washed with methanol. A crude product,2,3-dichloro-5,6-dicyano-p-benzoquinone (19 g, 84 mmol) and toluene (400mL) were mixed and stirred for one hour at 50 degrees C. After thereaction, methanol was added to the mixture and a precipitated solid wasseparated by filtration and refined by silica-gel column chromatography(eluent: toluene), so that a compound 12 (26 g, a yield of 51%) in aform of a white solid was obtained.

(3-2) Synthesis of Compound 13

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 12 (6.0 g, 13 mmol) in placeof the compound 5, so that a compound 13 (4.9 g, a yield of 69%) in aform of a white solid was obtained. As a result of FD-MS (FieldDesorption Mass Spectrometry) analysis, the reactant was identified asthe compound 13.

Synthesis Example 4: Synthesis of Compound 14

A synthesis scheme of a compound 14 is shown below.

(4-1) Synthesis of Compound 14

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 12 (5.0 g, 11 mmol) in placeof the compound 5 and the compound 8 (2.7 g, 13 mmol) in place of thecompound 6, so that a compound 14 (5.5 g, a yield of 93%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 14.

Synthesis Example 5: Synthesis of Compound 16

A synthesis scheme of a compound 16 is shown below.

(5-1) Synthesis of Compound 16

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 12 (5.0 g, 11 mmol) in placeof the compound 5 and the compound 15 (3.0 g, 13 mmol) in place of thecompound 6, so that a compound 16 (4.5 g, a yield of 74%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 16.

Synthesis Example 6: Synthesis of Compound 22

A synthesis scheme of a compound 22 is shown below.

(6-1) Synthesis of Compound 18

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 1 (20 g, 100 mmol) in place ofthe compound 5 and a compound 17 (22 g, 100 mmol) in place of thecompound 6, so that a compound 18 (25 g, a yield of 85%) in a form of awhite solid was obtained.

(6-2) Synthesis of Compound 20

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using 4-bromobenzaldehyde (a compound 19) (17 g,89 mmol) in place of the compound 2 and the compound 18 (25 g, 85 mmol)in place of the compound 1, so that a compound 20 (38 g, a yield of 97%)in a form of a white solid was obtained.

(6-3) Synthesis of Compound 21

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 20 (38 g, 82 mmol) in place ofthe compound 3, so that a compound 21 (16 g, a yield of 34%) in a formof a white solid was obtained.

(6-4) Synthesis of Compound 22

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 21 (5.0 g, 8.9 mmol) in placeof the compound 5, so that a compound 22 (3.9 g, a yield of 68%) in aform of a white solid was obtained. As a result of FD-MS (FieldDesorption Mass Spectrometry) analysis, the reactant was identified asthe compound 22.

Synthesis Example 7: Synthesis of Compound 24

A synthesis scheme of a compound 22 is shown below.

(7-1) Synthesis of Compound 24

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 21 (5.0 g, 8.9 mmol) in placeof the compound 5 and a compound 23 (2.8 g, 9.8 mmol) in place of thecompound 6, so that a compound 24 (25 g, a yield of 78%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 24.

Synthesis Example 8: Synthesis of Compound 28

A synthesis scheme of a compound 28 is shown below.

(8-1) Synthesis of Compound 26

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using the compound 19 (20 g, 109 mmol) in placeof the compound 2 and a compound 25 (25 g, 106 mmol) in place of thecompound 1, so that a compound 26 (27 g, a yield of 64%) in a form of awhite solid was obtained.

(8-2) Synthesis of Compound 27

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 26 (27 g, 68 mmol) in place ofthe compound 3, so that a compound 27 (6.7 g, a yield of 20%) in a formof a white solid was obtained.

(8-3) Synthesis of Compound 28

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 27 (3.4 g, 6.8 mmol) in placeof the compound 5, so that a compound 28 (3.3 g, a yield of 82%) in aform of a white solid was obtained. As a result of FD-MS (FieldDesorption Mass Spectrometry) analysis, the reactant was identified asthe compound 28.

Synthesis Example 9: Synthesis of Compound 31

A synthesis scheme of a compound 31 is shown below.

(9-1) Synthesis of Compound 29

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using the compound 19 (23 g, 125 mmol) in placeof the compound 2, so that a compound 29 (41 g, a yield of 95%) in aform of a white solid was obtained.

(9-2) Synthesis of Compound 30

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 29 (20 g, 55 mmol) in place ofthe compound 3, so that a compound 30 (15 g, a yield of 61%) in a formof a white solid was obtained.

(9-3) Synthesis of Compound 31

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using a compound 30 (6.9 g, 15 mmol) in place ofthe compound 5 and using 2.1 mol equivalent weight of the compound 6relative to the compound 30, so that a compound 31 (5.3 g, a yield of56%) in a form of a white solid was obtained. As a result of FD-MS(Field Desorption Mass Spectrometry) analysis, the reactant wasidentified as the compound 31.

Synthesis Example 10: Synthesis of Compound 34

A synthesis scheme of a compound 34 is shown below.

(10-1) Synthesis of Compound 32

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 19 (20 g, 108 mmol) in placeof the compound 3 and using 2 mol equivalent weight of the compound 4relative to the compound 19, so that a compound 32 (11 g, a yield of26%) in a form of a white solid was obtained.

(10-2) Synthesis of Compound 34

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 32 (5.5 g, 14 mmol) in placeof the compound 5 and using a compound 33 (4.9 g, 17 mmol) in place ofthe compound 6, so that a compound 34 (6.1 g, a yield of 78%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound34.

Synthesis Example 11: Synthesis of Compound 38

A synthesis scheme of a compound 38 is shown below.

(11-1) Synthesis of Compound 36

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using a compound 35 (28 g, 105 mmol) in place ofthe compound 2, so that a compound 36 (44 g, a yield of 98%) in a formof a white solid was obtained.

(11-2) Synthesis of Compound 37

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 36 (44 g, 98 mmol) in place ofthe compound 3, so that a compound 37 (17 g, a yield of 23%) in a formof a white solid was obtained.

(11-3) Synthesis of Compound 38

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 37 (5.0 g, 9.2 mmol) in placeof the compound 5 and using 3.1 mol equivalent weight of the compound 6relative to the compound 37, so that a compound 38 (4.7 g, a yield of64%) in a form of a white solid was obtained. As a result of FD-MS(Field Desorption Mass Spectrometry) analysis, the reactant wasidentified as the compound 38.

Synthesis Example 12: Synthesis of Compound 42

A synthesis scheme of a compound 42 is shown below.

(12-1) Synthesis of Compound 40

The compound 11 (11 g, 31 mmol), 1-phenacylpyridinium bromide (acompound 39) (8.7 g, 31 mmol) and ammonium acetate (19 g, 250 mmol) weresuspended in acetic acid (27 mL) and heated to reflux for 12 hours.After the reaction, the reactant solution was cooled to the roomtemperature, added with water and extracted with toluene. The obtainedorganic layer was washed with a 10-mass % aqueous sodium hydroxide andsaturated saline in sequential order and dried with sodium sulfate. Thesolvent was distilled away under reduced pressure. The residue was addedwith ethanol and heated to reflux to be dissolved. The reactant solutionwas cooled and precipitated in a crystal form. The crystal was separatedby filtration and washed with ethanol. Subsequently, the obtained solidwas dried under reduced pressure, so that a compound 40 (13 g, a yieldof 88%) in a form of a light-yellow solid was obtained.

(12-2) Synthesis of Compound 42

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 40 (5.0 g, 11 mmol) in placeof the compound 5 and a compound 41 (3.8 g, 12 mmol) in place of thecompound 6, so that a compound 42 (4.4 g, a yield of 62%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 42.

Synthesis Example 13: Synthesis of Compound 46

A synthesis scheme of a compound 46 is shown below.

(13-1) Synthesis of Compound 44

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using a compound 43 (9.8 g, 81 mmol) in place ofthe compound 1 and the compound 19 (16 g, 85 mmol) in place of thecompound 2, so that a compound 44 (9.5 g, a yield of 41%) in a form of alight-yellow solid was obtained.

(13-2) Synthesis of Compound 45

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 44 (9.5 g, 33 mmol) in placeof the compound 3, so that a compound 45 (3.5 g, a yield of 27%) in aform of a white solid was obtained.

(13-3) Synthesis of Compound 46

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 45 (3.5 g, 9.0 mmol) in placeof the compound 5 and the compound 23 (2.9 g, 9.9 mmol) in place of thecompound 6, so that a compound 46 (2.9 g, a yield of 58%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 46.

Synthesis Example 14: Synthesis of Compound 50

A synthesis scheme of a compound 50 is shown below.

(14-1) Synthesis of Compound 48

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using a compound 47 (37 g, 191 mmol) in place ofthe compound 1 and using the compound 35 (50 g, 191 mmol) in place ofthe compound 2, so that a compound 48 (82 g, a yield of 98%) in a formof a yellow solid was obtained.

(14-2) Synthesis of Compound 49

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 48 (82 g, 186 mmol) in placeof the compound 3, so that a compound 49 (40 g, a yield of 40%) in aform of a white solid was obtained.

(14-3) Synthesis of Compound 50

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 49 (6.0 g, 11 mmol) in placeof the compound 5 and using 2.2 mol equivalent weight of the compound 6relative to the compound 49, so that a compound 50 (4.2 g, a yield of53%) in a form of a white solid was obtained. As a result of FD-MS(Field Desorption Mass Spectrometry) analysis, the reactant wasidentified as the compound 50.

Synthesis Example 15: Synthesis of Compound 51

A synthesis scheme of a compound 51 is shown below.

(15-1) Synthesis of Compound 51

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 21 (6.0 g, 11 mmol) in placeof the compound 5 and using the compound 8 (2.7 g, 13 mmol) in place ofthe compound 6, so that a compound 51 (2.7 g, a yield of 39%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound51.

Synthesis Example 16: Synthesis of Compound 52

A synthesis scheme of a compound 52 is shown below.

(16-1) Synthesis of Compound 52

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 27 (6.0 g, 12 mmol) in placeof the compound 5 and the compound 8 (3.0 g, 14 mmol) in place of thecompound 6, so that a compound 52 (5.6 g, a yield of 79%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 52.

Synthesis Example 17: Synthesis of Compound 53

A synthesis scheme of a compound 53 is shown below.

(17-1) Synthesis of Compound 53

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 49 (6.0 g, 11 mmol) in placeof the compound 5 and using the compound 8 (5.2 g, 24 mmol) in place ofthe compound 6, so that a compound 53 (4.9 g, a yield of 61%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound53.

Synthesis Example 18: Synthesis of Compound 59

A synthesis scheme of a compound 59 is shown below.

(18-1) Synthesis of Compound 56

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 54 (54 g, 176 mmol) in placeof the compound 5 and using the compound 55 (32 g, 194 mmol) in place ofthe compound 6, so that a compound 56 (58 g, a yield of 95%) in a formof a white solid was obtained.

(18-2) Synthesis of Compound 57

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using the compound 56 (42 g, 122 mmol) in placeof the compound 1 and using 4-bromobenzaldehyde (the compound 19) (24 g,128 mmol) in place of the compound 2, so that a partially refinedproduct (78 g) of a compound 57 in a form of a yellow solid wasobtained. Without further refining the product, the subsequent reactionwas performed.

(18-3) Synthesis of Compound 58

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the partially refined product (78 g) of thecompound 57 in place of the compound 3, so that a compound 58 (27 g, ayield of 36%) in a form of a white solid was obtained.

(18-4) Synthesis of Compound 59

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 58 (6.0 g, 9.8 mmol) in placeof the compound 5, so that a compound 59 (3.2 g, a yield of 47%) in aform of a white solid was obtained. As a result of FD-MS (FieldDesorption Mass Spectrometry) analysis, the reactant was identified asthe compound 59.

Synthesis Example 19: Synthesis of Compound 64

A synthesis scheme of a compound 64 is shown below.

(19-1) Synthesis of Compound 61

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 1 (50 g, 251 mmol) in place ofthe compound 5 and using the compound 60 (66 g, 276 mmol) in place ofthe compound 6, so that a compound 61 (72 g, a yield of 92%) in a formof a white solid was obtained.

(19-2) Synthesis of Compound 62

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using the compound 61 (72 g, 230 mmol) in placeof the compound 1 and using 4-bromobenzaldehyde (the compound 19) (43 g,230 mmol) in place of the compound 2, so that a compound 62 (107 g, ayield of 97%) in a form of a white solid was obtained.

(19-3) Synthesis of Compound 63

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 62 (107 g, 223 mmol) in placeof the compound 3, so that a compound 63 (47 g, a yield of 36%) in aform of a white solid was obtained.

(19-4) Synthesis of Compound 64

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 63 (7.0 g, 12 mmol) in placeof the compound 5, so that a compound 64 (4.9 g, a yield of 61%) in aform of a white solid was obtained. As a result of FD-MS (FieldDesorption Mass Spectrometry) analysis, the reactant was identified asthe compound 64.

Synthesis Example 20: Synthesis of Compound 65

A synthesis scheme of a compound 65 is shown below.

(20-1) Synthesis of Compound 65

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 63 (7.0 g, 12 mmol) in placeof the compound 5 and the compound 8 (2.8 g, 13 mmol) in place of thecompound 6, so that a compound 65 (4.3 g, a yield of 53%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 65.

Synthesis Example 21: Synthesis of Compound 69

A synthesis scheme of a compound 69 is shown below.

(21-1) Synthesis of Compound 68

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using a compound 66 (7.7 g, 72 mmol) in place ofthe compound 3 and using the compound 67 (34 g, 145 mmol) in place ofthe compound 4, so that a compound 68 (9.4 g, a yield of 32%) in a formof a white solid was obtained.

(21-2) Synthesis of Compound 69

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 68 (4.5 g, 9.6 mmol) in placeof the compound 5 and using 2.2 mol equivalent weight of the compound 6relative to the compound 68, so that a compound 69 (4.4 g, a yield of71%) in a form of a white solid was obtained. As a result of FD-MS(Field Desorption Mass Spectrometry) analysis, the reactant wasidentified as the compound 69.

Synthesis Example 21: Synthesis of Compound 70

A synthesis scheme of a compound 70 is shown below.

(22-1) Synthesis of Compound 70

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 68 (4.9 g, 10 mmol) in placeof the compound 5 and using the compound 8 (4.9 g, 23 mmol) in place ofthe compound 6, so that a compound 70 (3.1 g, a yield of 46%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound70.

Synthesis Example 23: Synthesis of Compound 71

A synthesis scheme of a compound 71 is shown below.

(23-1) Synthesis of Compound 71

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 68 (4.5 g, 9.6 mmol) in placeof the compound 5 and using the compound 15 (4.8 g, 21 mmol) in place ofthe compound 6, so that a compound 71 (3.4 g, a yield of 53%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound71.

Synthesis Example 24: Synthesis of Compound 72

A synthesis scheme of a compound 72 is shown below.

(24-1) Synthesis of Compound 72

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 49 (10 g, 18 mmol) in place ofthe compound 5 and using the compound 15 (9.3 g, 41 mmol) in place ofthe compound 6, so that a compound 72 (9.7 g, a yield of 70%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound72.

Synthesis Example 25: Synthesis of Compound 74

A synthesis scheme of a compound 74 is shown below.

(25-1) Synthesis of Compound 74

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 49 (10 g, 18 mmol) in place ofthe compound 5 and using the compound 73 (9.3 g, 41 mmol) in place ofthe compound 6, so that a compound 74 (9.5 g, a yield of 68%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound74.

Synthesis Example 26: Synthesis of Compound 78

A synthesis scheme of a compound 78 is shown below.

(26-1) Synthesis of Compound 76

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using the compound 75 (38 g, 193 mmol) in placeof the compound 1 and the compound 35 (50 g, 189 mmol) in place of thecompound 2, so that a compound 76 (75 g, a yield of 89%) in a form of awhite solid was obtained.

(26-2) Synthesis of Compound 77

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 76 (71 g, 158 mmol) in placeof the compound 3, so that a compound 77 (31 g, a yield of 33%) in aform of a white solid was obtained.

(26-3) Synthesis of Compound 78

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 77 (15 g, 28 mmol) in place ofthe compound 5 and using 3.5 equivalent weight of the compound 6relative to the compound 77, so that a compound 78 (5.0 g, a yield of23%) in a form of a white solid was obtained. As a result of FD-MS(Field Desorption Mass Spectrometry) analysis, the reactant wasidentified as the compound 78.

Synthesis Example 27: Synthesis of Compound 79

A synthesis scheme of a compound 79 is shown below.

(27-1) Synthesis of Compound 79

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 77 (15 g, 28 mmol) in place ofthe compound 5 and using the compound 8 (20 g, 96 mmol) in place of thecompound 6, so that a compound 79 (12 g, a yield of 52%) in a form of awhite solid was obtained. As a result of FD-MS (Field Desorption MassSpectrometry) analysis, the reactant was identified as the compound 79.

Synthesis Example 28: Synthesis of Compound 82

A synthesis scheme of a compound 82 is shown below.

(28-1) Synthesis of Compound 80

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using the compound 25 (34 g, 144 mmol) in placeof the compound 1 and using the compound 35 (42 g, 158 mmol) in place ofthe compound 2, so that a compound 80 (69 g, a yield of 100%) in a formof a light-brown solid was obtained.

(28-2) Synthesis of Compound 81

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 80 (69 g, 144 mmol) in placeof the compound 3, so that a compound 81 (18 g, a yield of 22%) in aform of a light-yellow solid was obtained.

(28-3) Synthesis of Compound 82

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 81 (9.1 g, 16 mmol) in placeof the compound 5 and using 2.2 mol equivalent weight of the compound 6relative to the compound 81, so that a compound 82 (9.4 g, a yield of79%) in a form of a light-yellow solid was obtained. As a result ofFD-MS (Field Desorption Mass Spectrometry) analysis, the reactant wasidentified as the compound 82.

Synthesis Example 29: Synthesis of Compound 83

A synthesis scheme of a compound 83 is shown below.

(29-1) Synthesis of Compound 83

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 81 (9.0 g, 15 mmol) in placeof the compound 5 and using the compound 8 (7.2 g, 34 mmol) in place ofthe compound 6, so that a compound 83 (8.1 g, a yield of 69%) in a formof a light-yellow solid was obtained. As a result of FD-MS (FieldDesorption Mass Spectrometry) analysis, the reactant was identified asthe compound 83.

Synthesis Example 30: Synthesis of Compound 88

A synthesis scheme of a compound 88 is shown below.

(30-1) Synthesis of Compound 85

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 19 (50 g, 270 mmol) in placeof the compound 5 and using the compound 84 (56 g, 325 mmol) in place ofthe compound 6, so that a compound 85 (53 g, a yield of 85%) in a formof a white solid was obtained.

(30-2) Synthesis of Compound 86

Synthesis was made by the same method as in (1-1) synthesis of thecompound 7, except for using the compound 10 (65 g, 235 mmol) in placeof the compound 1 and using the compound 85 (53 g, 229 mmol) in place ofthe compound 2, so that a compound 86 (109 g) in a form of alight-yellow solid was obtained.

(30-3) Synthesis of Compound 87

Synthesis was made by the same method as in (1-2) synthesis of thecompound 7, except for using the compound 86 (108 g, 221 mmol) in placeof the compound 3, so that a compound 87 (44 g, a yield of 34%) in aform of a white solid was obtained.

(30-4) Synthesis of Compound 88

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 87 (6.0 g, 10 mmol) in placeof the compound 5 and using the compound 15 (2.8 g, 12 mmol) in place ofthe compound 6, so that a compound 88 (5.9 g, a yield of 84%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound88.

Synthesis Example 31: Synthesis of Compound 89

A synthesis scheme of a compound 89 is shown below.

(31-1) Synthesis of Compound 89

Synthesis was made by the same method as in (1-3) synthesis of thecompound 7, except for using the compound 87 (6.0 g, 10 mmol) in placeof the compound 5 and using the compound 73 (2.8 g, 12 mmol) in place ofthe compound 6, so that a compound 89 (6.4 g, a yield of 91%) in a formof a white solid was obtained. As a result of FD-MS (Field DesorptionMass Spectrometry) analysis, the reactant was identified as the compound89.

Manufacturing of Organic EL Device

For manufacturing the organic EL device, the following compounds wereused in addition to the compounds synthesized in the above SynthesisExamples.

Example 1

A glass substrate (size: 25 mm×75 mm×0.7 mm thick, manufactured byGeomatec Co., Ltd.) having an ITO transparent electrode (anode) wasultrasonic-cleaned in isopropyl alcohol for five minutes, and thenUV/ozone-cleaned for 30 minutes. After the glass substrate having thetransparent electrode line was cleaned, the glass substrate was mountedon a substrate holder of a vacuum evaporation apparatus. Initially, acompound HI-1 was evaporated on a surface of the glass substrate wherethe transparent electrode line was provided in a manner to cover thetransparent electrode, thereby forming a 5-nm thick HI-1 film. The HI-1film serves as a hole injecting layer.

After the formation of the HT-1 film, a compound HT-1 was evaporated onthe HT-1 film to form an 80-nm thick HT-1 film. The HT-1 film serves asa first hole transporting layer.

After the film formation of the HT-1 film, a compound HT-2 wasevaporated on the HT-1 film to form a 15-nm thick HT-2 film on the HT-1film. The HT-2 film serves as a second hole transporting layer.

A compound BH-1 (host material) and a compound BD-1 (dopant material)(mass ratio of BH-1 to BD-1 was 20:1) were co-evaporated on the HT-2film to form a 25-nm thick emitting layer.

The compound 7 was evaporated on this emitting layer to form a 20-nmthick blocking layer.

A compound ET-1 (electron transporting material) was evaporated on theblocking layer to form a 5-nm thick electron injecting layer.

LiF was evaporated on the electron injecting layer to form a 1-nm thickLiF film.

A metal Al was evaporated on the LiF film to form an 80-nm thick metalcathode.

Thus, the organic EL device of Example 1 was manufactured.

Examples 2 to 19 and Comparative 1

Organic EL devices of Examples 2 to 19 and Comparative 1 weremanufactured in the same manner as the organic EL device in the Example1, except for using materials shown in Table 1 as a material for theblocking layer. BCP shown below was used as the material for theblocking layer of the organic EL device in Comparative 1.

Evaluation of Device

The manufactured organic EL devices were evaluated as below. The resultsare shown in Table 1.

Initial Performance

Voltage was applied to the organic EL device so that a current densitybecomes 10 mA/cm², and a voltage value (V) at that time was measured. ELspectra were measured with a spectral radiance meter (CS-1000,manufactured by KONICA MINOLTA). Chromaticity CIE_(x), CIE_(y), currentefficiency L/J(cd/A) and external quantum efficiency EQE (%) werecalculated from the obtained spectral-radiance spectra.

Measurement of TTF Ratio

When the triplet energy of the host material, the dopant material andthe blocking layer material satisfies a predetermined relation, theratio of luminous intensity derived from TTF relative to the entireemission can be high, so that a fluorescent device can be highlyefficient to the level unachievable by a typically known fluorescentdevice.

The ratio of luminous intensity derived from TTF is measurable by atransitional EL method. The transitional EL method is a method formeasuring reduction behavior (transitional property) of EL emissionafter DC voltage applied on the device is removed. EL luminous intensityare classified into a luminescence component from singlet excitonsgenerated in first recombination and a luminescence component fromsinglet excitons generated through TTF phenomenon. Since lifetime of thesinglet excitons is very short at nano-second order, EL emission israpidly reduced after removal of DC voltage.

On the other hand, since the TTF phenomenon provides emission fromsinglet excitons generated through long-life triplet excitons, ELemission is gradually reduced. Thus, since there is a large differencein time between emission from the singlet excitons and emission from thetriplet excitons, luminous intensity derived from TTF is obtainable.Specifically, the luminous intensity can be determined by the followingmethod.

Transitional EL waveform is measured as follows (see FIG. 13). Pulsevoltage waveform output from a voltage pulse generator (PG) is appliedon an EL device. The applied voltage waveform is loaded in anoscilloscope (OSC). When a pulse voltage is applied on the EL device,the EL device generates pulse emission. This emission is loaded in theoscilloscope (OSC) through a photomultiplier (PMT). The voltage waveformand the pulse emission are synchronized and loaded in a personalcomputer (PC).

The ratio of luminous intensity derived from TTF is determined asfollows based on analysis of the transitional EL waveform.

A rate equation for reduction behavior of triplet excitons is resolvedand the reduction behavior of luminous intensity based on TTF phenomenonis brought into modeling. Time-varying reduction of a density n_(T) oftriplet excitons within the emitting layer is represented by thefollowing rate equation using a reduction speed α due to lifetime of thetriplet excitons and a reduction speed γ due to collision of the tripletexcitons.

$\begin{matrix}{\frac{{dn}_{T}}{dt} = {{{- \alpha} \cdot n_{T}} - {\gamma \cdot n_{T}^{2}}}} & \left\lbrack {{Formula}\mspace{14mu} 1} \right\rbrack\end{matrix}$

When this differential formula is approximately resolved, the followingformula is obtained. Herein, I_(TTF) represents luminous intensityderived from TTF. A is a constant. Thus, when the transitional ELemission is based on TTF, a reciprocal number of the square root ofintensity of the transitional EL emission is shown approximately in alinear line. The measured transitional EL waveform data is fit in thefollowing approximate expression to obtain the constant A. At this time,luminous intensity 1/A² at the time t=0 when DC voltage is removed isdefined as the ratio of luminous intensity derived from TTF.

$\begin{matrix}{\frac{1}{\sqrt{I_{TTF}}} \propto {A + {\gamma \cdot t}}} & \left\lbrack {{Formula}\mspace{14mu} 2} \right\rbrack\end{matrix}$

A graph of FIG. 14(A) shows a measurement example where a predeterminedDC voltage is applied on the EL device and then the DC voltage isremoved and shows time-varying luminous intensity of the EL device. TheDC voltage was removed at the time of about 3×10⁻⁸ seconds in the graphof FIG. 14(A). In the graph, the luminous intensity when voltage isremoved is defined as 1. After rapid reduction before the elapse ofabout 2×10⁻⁷, a gradual reduction component appears. In the graph ofFIG. 14(B), the voltage removal time is a starting point and thereciprocal numbers of the square root of luminous intensity before theelapse of 10⁻⁵ seconds after voltage removal are plotted in anapproximately linear line. A value at an intersection A of the ordinateaxis and the linear line extended to the starting point is 2.41.Accordingly, the ratio of luminous intensity derived from TTF obtainedfrom the transitional EL waveform is 1/2.41²=0.17, which means 17% ofthe entire luminous intensity is derived from TTF.

The luminous intensity is preferably fitted in a linear line by themethod of least squares. In this case, the luminous intensity before theelapse of 10⁻⁵ seconds is preferably fitted.

Voltage pulse waveform (pulse width: 500 micro second, frequency: 20 Hz,voltage: equivalent to 0.1 to 100 mA/cm²) output from a pulse generator(8114A: manufactured by Agilent Technologies) was applied. EL emissionwas input in a photomultiplier (R928: manufactured by HamamatsuPhotonics K.K.). The pulse voltage waveform and the EL emission weresynchronized and loaded in an oscilloscope (2440: Tektronix) to obtain atransitional EL waveform. The transitional EL waveform was analyzed todetermine a TTF ratio.

Voltage was applied on the organic EL device of Example 1 at the roomtemperature. The pulse voltage was removed at the time of about 3×10⁻⁸seconds.

Based on the graph, where the voltage removal time was a starting pointand the reciprocal numbers of the square root of luminous intensitybefore the elapse of 1.5×10⁻⁵ seconds after voltage removal wereplotted, the TTF ratio was obtained. The same measurement was performedin other Examples and Comparatives. The results are shown in Table 1.

TABLE 1 Blocking layer Voltage Chromaticity CIE L/J EQE TTF Ratiomaterial (V) x y (cd/A) (%) (%) Example 1 Compound 7 3.38 0.144 0.13110.32 9.21 28 Example 2 Compound 9 3.51 0.142 0.137 10.39 9.06 32Example 3 Compound 13 3.65 0.142 0.151 10.63 8.64 33 Example 4 Compound14 3.52 0.145 0.131 9.84 8.76 29 Example 5 Compound 16 3.55 0.145 0.1279.76 8.81 32 Example 6 Compound 22 3.61 0.143 0.137 11.09 9.65 32Example 7 Compound 31 3.75 0.143 0.134 10.05 8.87 35 Example 8 Compound50 4.08 0.144 0.128 9.76 8.87 29 Example 9 Compound 51 3.59 0.143 0.13711.10 9.64 31 Example 10 Compound 52 3.81 0.143 0.132 11.17 9.96 33Example 11 Compound 53 4.15 0.143 0.134 11.03 9.72 33 Example 12Compound 24 3.71 0.143 0.131 10.53 9.42 30 Example 13 Compound 72 3.810.141 0.138 10.03 8.74 32 Example 14 Compound 74 3.64 0.143 0.135 11.349.96 30 Example 15 Compound 78 3.75 0.142 0.130 11.04 9.96 31 Example 16Compound 79 4.02 0.142 0.132 10.50 9.40 34 Example 17 Compound 83 3.780.143 0.134 11.21 9.87 36 Example 18 Compound 88 3.58 0.142 0.136 11.059.69 31 Example 19 Compound 89 3.56 0.143 0.135 10.78 9.43 28 Comp. 1BCP 4.30 0.144 0.128 8.43 7.65 25

Since the aromatic heterocyclic compound of the invention was used forthe blocking layer of the organic EL devices of Examples 1 to 19, theorganic EL devices of Examples 1 to 19 exhibited a higher TTF ratio, ahigher current efficiency and a higher external quantum efficiency thanthe organic EL device of Comparative 1. Moreover, a drive voltage of theorganic EL devices of Examples 1 to 19 was also lower than that of theorganic EL device of Comparative 1.

INDUSTRIAL APPLICABILITY

An organic EL device of the invention is applicable to a display and anilluminator.

EXPLANATION OF CODES

-   -   1,2,3,4,5 organic EL device    -   10 anode    -   20, 22, 24 emitting layer    -   30, 32 blocking layer    -   40 electron injecting layer    -   41 electron transporting layer    -   50 cathode    -   60 hole transporting zone    -   70 electron transporting zone

The invention claimed is:
 1. An aromatic heterocyclic derivative offormula (4):

wherein: X₁, X₂ and X₃ are each a nitrogen atom; Ar₂ is an unsubstitutedterphenyl group; Ar₁ and A are represented by a formula (5) below,(HAr)_(a)-L₁-  (5) wherein: HAr is represented by a formula (6) below; ais 1; L₁ is a single bond;

wherein: Y₁ is an oxygen atom; X₁₁ and X₁₈ are each CR₁₃; one of X₁₂ andX₁₇ is a carbon atom bonded to a carbon atom of the 6 membered ring offormula (4) by L₁ as a single bond and the other of X₁₂ and X₁₇ is CR₁₃and X₁₃ to X₁₆ are each CR₁₃; and R₁₃ is a hydrogen atom.
 2. An organicelectroluminescence device comprising: an anode; and a cathode; whereinthe aromatic heterocyclic derivative represented by the formula (4)according to claim 1 is present between the anode and the cathode. 3.The organic electroluminescence device according to claim 2, furthercomprising: an emitting layer between the anode and the cathode; whereinthe emitting layer comprises the aromatic heterocyclic derivative. 4.The organic electroluminescence device according to claim 3, wherein theemitting layer comprises a phosphorescent dopant.
 5. The organicelectroluminescence device according to claim 3, wherein the emittinglayer comprises the heterocyclic derivative of formula (4) according toclaim
 1. 6. The aromatic heterocyclic derivative of formula (4)according to claim 1, wherein Ar₂ is of one of the following formulae:


7. The aromatic heterocyclic derivative of formula (4) according toclaim 6, wherein Ar₂ is


8. The aromatic heterocyclic derivative of formula (4) according toclaim 6, wherein Ar₂ is